Electroluminiscent metal complexes with dibenzo[f,h] quinoxalines

ABSTRACT

This invention relates to electroluminescent metal complexes of the formula (I), or (II), a process for their preparation, electronic devices comprising the metal complexes and their use in electronic devices, especially organic light emitting diodes (OLEDs), as oxygen sensitive indicators, as phosphorescent indicators in bioassays, and as catalysts.

This invention relates to electroluminescent metal complexes withdibenzo[f,h]quinoxalines, a process for their preparation, electronicdevices comprising the metal complexes and their use in electronicdevices, especially organic light emitting diodes (OLEDs), as oxygensensitive indicators, as phosphorescent indicators in bioassays, and ascatalysts.

Organic electronic devices that emit light, such as light-emittingdiodes that make up displays, are present in many different kinds ofelectronic equipment. In all such devices, an organic active layer issandwiched between two electrical contact layers. At least one of theelectrical contact layers is light-transmitting so that light can passthrough the electrical contact layer. The organic active layer emitslight through the light-transmitting electrical contact layer uponapplication of electricity across the electrical contact layers.

It is well known to use organic electroluminescent compounds as theactive component in light-emitting diodes. Simple organic molecules suchas anthracene, thiadiazole derivatives, and coumarin derivatives areknown to show electroluminescence. Semiconductive conjugated polymershave also been used as electroluminescent components, as has beendisclosed in, for example, in U.S. Pat. Nos. 5,247,190, 5,408,109 andEP-A-443 861. Complexes of 8-hydroxyquinolate with trivalent metal ions,particularly aluminum, have been extensively used as electroluminescentcomponents, as has been disclosed in, for example, U.S. Pat. No.5,552,678.

Burrows and Thompson have reported that fac-tris(2-phenylpyridine)iridium can be used as the active component in organic light-emittingdevices. (Appl. Phys. Lett. 1999, 75, 4.) The performance is maximizedwhen the iridium compound is present in a host conductive material.Thompson has further reported devices in which the active layer ispoly(N-vinyl carbazole) doped withfac-tris[2-(4′,5′-difluorophenyl)pyridine-C′²,N]iridium(III). (PolymerPreprints 2000, 41(1), 770.)

JP2005298483 describes an iridium complex, such as, for example,

which can be used for the luminous element and is also suitable for anorganic electroluminescent element material, an electrochemiluminescent(ECL) element material, a luminescence sensor, a photosensitizer, adisplay, etc., its preparation method and a luminous material.

KR20060079625 relates to phosphorescent red-emitting iridium complexes,such as, for example,

and organic electroluminescent device comprising same. Z. Liu et al,Adv. Funct. Mat. 2006, 16, 1441, describe the use of the complexes

wherein R¹ is t-butyl and R² is

or R¹ is t-butyl and R² is

for highly efficient non-doped organic light emitting diodes.

J.-P. Duan et al., Adv. Mat. 2003, 15, 224, describe the use of thecomplexes

as orange-red emitters in an OLED.

KR20060036670 relates to phosphorescent iridium complexes and organicelectroluminescent devices comprising the same. The followingphosphorescent iridium complexes are explicitly disclosed

EP1939208A1, which enjoys an earlier priority than the presentinvention, but has been published after the priority date of the presentinvention, is directed to an organometallic complex having a structurerepresented by the general formula

-   wherein Ar represents an aryl group having 6 to 25 carbon atoms;-   A¹ represents any one of hydrogen, an alkyl group having 1 to 4    carbon atoms, and an alkoxy group having 1 to 4 carbon atoms;-   A² to A⁸ each represent any one of hydrogen, an alkyl group having 1    to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a    halogen group;-   M₁₀ represents a metal of Group 9 elements and Group 10 elements;-   L₁₀ represents a monoanionic ligand; and-   u is 2 when the metal is a Group 9 element, and u is 1 when the    metal is a Group 10 element.

WO2005049762 relates to a light-emitting device comprising at least asubstrate, an anode, a light-emitting layer and a cathode whereby thelight-emitting layer contains an iridium complex IrL3 and whereby atleast two ligands L are a dibenzoquinoline. WO2005049762 relates inparticular to the complexesIr(dibenzo[f,h]quinoline)₂(pentane-2,4-dionate) andIr(dibenzo[f,h]quinoline)₃ which emit light with a wavelength ofλ_(max)=545 nm and λ_(max)=595 nm respectively:

However, there is a continuing need for electroluminescent compounds,especially orange, or red emitters, having improved performance, such asfor example, compounds having high emission efficiency, excellentvaporizability, thermal stability, processing stability, high chargecarrier mobilities, low turn-on voltage and high temperature stabilityof the emission color.

Accordingly the present invention is directed to compounds (metalcomplexes) of the formula

wherein

-   R¹, R² and R^(1′) are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₁-C₁₈perfluoroalkyl, C₅-C₁₂cycloalkyl, which can optionally be    substituted by one to three C₁-C₄alkyl groups, C₆-C₂₄aryl,    C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,    C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,    C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E    and/or interrupted by D, C₇-C₂₅arylalkyl, CN,

-    —CO—R²⁸, or-   R¹ and R² together form a ring,-   R³, R⁸, R^(3′) and R^(8′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which    is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is    substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,    C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,    C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

-    —NR²⁵R²⁶, —SR²⁹, or Si(R³⁰)₃,-   R⁴, R⁷, R^(4′) and R^(7′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₁-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which    is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is    substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,    C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,    C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

-    —NR²⁵R²⁶, —SR²⁹, or Si(R³⁰)₃,-   R⁵, R⁶, R^(5′) and R^(6′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₁-C₁₈ perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl    which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which    is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,    C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,    C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

-    —NR²⁵R²⁶, —SR²⁹, Si(R³⁰)₃,-   R²⁵ and R²⁶ are independently of each other C₁-C₁₈alkyl, C₁-C₁₈alkyl    which is substituted by E and/or interrupted by D, C₆-C₂₄aryl,    C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,    C₂-C₂₀heteroaryl which is substituted by G, or-   R²⁵ and R²⁶ together with the nitrogen atom to which they are bonded    form a heteroaromatic ring, or ring system, which may optionally be    substituted;-   BU is a bridging unit,-   D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR^(25′)—; —SiR³⁰R³¹—;    —POR³²—; —CR²³═CR²⁴—; or —C≡C—;-   E is —OR²⁸; —SR²⁸; —NR^(25′)R^(26′); —COR²⁸; —COOR²⁷;    —CONR^(25′)R^(26′); —CN; or halogen; G is E, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈ perfluoroalkyl,    C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substituted by E and/or    interrupted by D, or C₂-C₁₈alkenyl,-   R²³, R²⁴, R^(25′) and R^(26′) are independently of each other H;    C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or    C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by    —O—;-   R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl;    C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;    C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,-   R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by    C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is    interrupted by —O—,-   R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl,    or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and-   R³² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted    by C₁-C₁₈alkyl,-   M is Pd, Rh, or Re, especially Pt, or Ir,-   L is a mono-, or bi-dentate ligand,-   if L is a monodentate ligand,-   m is 0, or 2, and n is 1, or 2, if M is Pd, or Pt,-   m is 0, 2, or 4, and n is 1, 2, or 3, if M is Rh, Ir or Re,-   if L is a bidentate ligand,-   m is 0, or 1, and n is 1, or 2, if M is Pd, or Pt,-   m is 0, 1, or 2, and n is 1, 2, or 3, if M is Rh, Ir or Re,-   with the proviso that at least one of R¹, R², R³, R⁸, R⁴, R⁷, R⁵ and    R⁶ is different from H and the further proviso that

-    are excluded; and with the further proviso that organometallic    complexes having a structure represented by the general formula

-    are excluded,-   wherein Ar represents an aryl group having 6 to 25 carbon atoms;-   A¹ represents any one of hydrogen, an alkyl group having 1 to 4    carbon atoms, and an alkoxy group having 1 to 4 carbon atoms;-   A² to A⁸ each represent any one of hydrogen, an alkyl group having 1    to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a    halogen group;-   M₁₀ represents a metal of Group 9 elements and Group 10 elements;-   L₁₀ represents a monoanionic ligand; and-   u is 2 when the metal is a Group 9 element, and u is 1 when the    metal is a Group 10 element.

The compounds of the present invention are preferably orange, or redemitters having a λ_(max) above about 520 nm, especially above about 560nm and very especially above about 600 nm. The dibenzo[f,h]quinoxalinecompound or compounds should have a colour coordinate of between about(0.62, 0.37) and about (0.68, 0.32), especially a colour coordinate ofbetween about (0.63, 0.34) and about (0.68, 0.32), very especially aNTSC coordinate of about (0.65, 0.35) or (0.68, 0.32).

According to the present invention the metal complex comprise at least adibenzo[f,h]-quinoxaline ligand, i.e. it may comprise two or three ormore dibenzo[f,h]quinoxaline ligands.

The term “ligand” is intended to mean a molecule, ion, or atom that isattached to the coordination sphere of a metallic ion. The term“complex”, when used as a noun, is intended to mean a compound having atleast one metallic ion and at least one ligand. The term “group” isintended to mean a part of a compound, such a substituent in an organiccompound or a ligand in a complex. The term “facial” is intended to meanone isomer of a complex, Ma₃b₃, having octahedral geometry, in which thethree “a” groups are all adjacent, i.e. at the corners of one triangularface of the octahedron. The term “meridional” is intended to mean oneisomer of a complex, Ma₃b₃, having octahedral geometry, in which thethree “a” groups occupy three positions such that two are trans to eachother, i.e. the three “a” groups sit in three coplanar positions,forming an arc across the coordination sphere that can be thought of asa meridion. The phrase “adjacent to” when used to refer to layers in adevice, does not necessarily mean that one layer is immediately next toanother layer. The term “photoactive” refers to any material thatexhibits electroluminescence and/or photosensitivity.

The metal complexes of the present invention are characterized in thatat least one ligand is derived from a dibenzo[f,h]quinoxaline compound.Suitable dibenzo[f,h]quinoxalines, or intermediates thereof, are knownor can be produced according to known procedures. The synthesis ofsuitable dibenzo[f,h]quinoxaline and intermediates thereof is, forexample, described in J.-P. Duan et al., Adv. Mat. 2003, 15, 224 andWO2006/097419, as well as the references cited therein.

The metal M is selected from Ir, Rh and Re as well as Pt and Pd, whereinPt and Ir are most preferred.

Preferably, at least one of R³, R⁸, R⁴, R⁷, R⁵ and R⁶ is different fromH, in particular R³ and R⁸ or R⁴ and R⁷ or R⁵ and R⁶ are different fromH. More preferably R³ and R⁸ or R⁴ and R⁷ are different from H, mostpreferably R⁴ and R⁷ are different from H.

Preferably at least one of the substituents R³ and R⁸ or R⁴ and R⁷ or R⁵and R⁶ is different from H. More preferably at least one of thesubstituents R³ and R⁸ or R⁴ and R⁷ is different from H, most preferablyat least one of the substituents R⁴ and R⁷ is different from H.

In one embodiment of the present invention at least one of thesubstituents R³, R⁸, R⁴ and R⁷ is C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D.

In one embodiment of the present invention at least one of thesubstituents R³, R⁸, R⁴ and R⁷ is a group

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, R¹¹ can be same, ordifferent in each occurrence and is C₁-C₂₅alkyl, C₁-C₂₅alkoxy, orNR²⁵R²⁶. Preferably R³ and R⁸ or R⁴ and R⁷ are a group

More preferably R⁴ and R⁷ are a group

In one embodiment of the present invention at least one of thesubstituents R³, R⁸, R⁴ and R⁷ is a group —NR²⁵R²⁶, wherein R²⁵ and R²⁶are independently of each other especially phenyl, naphthyl, anthryl,biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can optionallybe substituted, such as

or R²⁵ and R²⁶ together with the nitrogen atom to which they are bondedform a heteroaromatic ring, or ring system, such as

m′ is 0, 1, or 2;

-   m″ can be the same or different at each occurence and is 0, 1, 2, or    3, especially 0, 1, or 2, very especially 0 or 1;-   R⁴¹ can be the same or different at each occurence and is Cl, F, CN,    N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a    C₁-C₂₅alkoxy group, in which one or more carbon atoms which are not    in neighbourhood to each other could be replaced by —NR⁴⁵—, —O—,    —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be    replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein    one or more carbon atoms can be replaced by O, S, or N, and/or which    can be substituted by one or more non-aromatic groups R⁴¹, or two or    more groups R⁴¹ form a ring system;-   R⁴⁵ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, in which    one or more carbon atoms which are not in neighbourhood to each    other could be replaced by —NR^(45″)—, —O—, —S—, —C(═O)—O—, or,    —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be    replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein    one or more carbon atoms can be replaced by O, S, or N, and/or which    can be substituted by one or more non-aromatic groups R⁴¹, and-   R^(45″) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group,-   R¹¹⁶, R¹¹⁷ and R^(117′) are independently of each other H, halogen,    —CN, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,    C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is    substituted by E and/or interrupted by D, C₇-C₂₅aralkyl,    —C(═O)—R¹²⁷, —C(═O)OR¹²⁷, or —C(═O)NR¹²⁷R¹²⁶, or-   substituents R¹¹⁶, R¹¹⁷ and R^(117′), which are adjacent to each    other, can form a ring,-   R¹¹⁹ and R¹²⁹ are independently of each other C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,    C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,    C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E    and/or interrupted by D, or C₇-C₂₅aralkyl, or-   R¹¹⁹ and R¹²⁰ together form a group of formula ═CR¹²¹R¹²², wherein-   R¹²¹ and R¹²² are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or    C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or-   R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which    optionally can be substituted by C₁-C₁₈alkyl, C₁-C₁₈alkyl which is    substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl    which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which    is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,    C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,    C₇-C₂₅aralkyl, or —C(═O)—R¹²⁷, and-   R¹²⁶ and R¹²⁷ are independently of each other H; C₆-C₁₈aryl;    C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;    C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,-   D is —CO—, —COO—, —S—, —SO—, —SO₂—, —O—, —NR⁶⁵—, —SiR⁷⁰R⁷¹—,    —POR⁷²—, —CR⁶³═CR⁶⁴—, or —C≡C—, and-   E is —OR⁶⁹, —SR⁶⁹, —NR⁶⁵R⁶⁶, —COR⁶⁸, —COOR⁶⁷, —CONR⁶⁵R⁶⁶, —CN, or    halogen,-   G is E, or C₁-C₁₈alkyl,-   R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are independently of each other H; C₆-C₁₈aryl;    C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, C₁-C₁₈alkoxy;    C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—; or-   R⁶⁵ and R⁶⁶ together form a five or six membered ring,-   R⁶⁷ and R⁶⁸ are independently of each other H; C₆-C₁₈aryl;    C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;    C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,-   R⁶⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by    C₁-C₁₈alkyl, C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is    interrupted by —O—,-   R⁷⁰ and R⁷¹ are independently of each other C₁-C₁₈alkyl, C₆-C₁₈aryl,    or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and-   R⁷² is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted    by C₁-C₁₈alkyl.

BU is a bridging unit, such as

wherein R¹¹⁹, R¹²⁰, R⁴¹ and m″ are as defined above.

In a preferred embodiment of the present invention R²⁵ and R²⁶ areindependently of each other

R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which mayoptionally be interrupted by —O—, or C₁-C₂₅alkoxy.

Examples of

(R⁴¹ is H, or C₁-C₈alkyl), and

Examples of groups

are shown below:

wherein R⁴¹, R¹¹⁶, R¹¹⁷, R¹¹⁹, R¹²⁰ and m″ are as defined above.

Compounds of the formula I, or II are preferred, wherein

-   R¹, R^(1′) and R² are independently of each other H, C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, which can optionally be substituted by one to    three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted    by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,

-    or CN, or-   R¹ and R² together form a group

-   R^(206′), R^(208′), R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹ and R²¹⁰ and R²¹⁰    are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, or    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl or    C₁-C₁₈alkoxy;-   R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁷ and R³⁰⁸ are independently    of each other H, or C₁-C₁₈alkyl,-   R³, R⁸, R^(3′) and R^(8′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,    C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E    and/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, or —NR²⁵R²⁶;-   R⁴, R⁷, R^(4′) and R^(7′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,    C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    C₂-C₁₈alkenyl, C₁-C₁₈alkoxy which is substituted by E and/or    interrupted by —O—, C₇-C₂₅arylalkyl, CN, —NR²⁵R²⁶;-   R⁵, R⁶, R^(5′) and R^(6′) are H,-   R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl    which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl;    or C₁-C₁₈alkyl which is interrupted by —O—; or-   R²⁵ and R²⁶ together with the nitrogen atom to which they are bonded    form a heteroaromatic ring system

-    m″, m′ and R⁴¹ are as defined below;-   E is —OR²⁶; —SR²⁹; —NR^(25′)R^(26′), CN, or F; G is E, CF₃,    C₁-C₁₈alkyl, or C₂-C₁₈alkenyl,-   M is Pd, Rh, or Re, especially Pt, or Ir,-   L is a bidentate ligand,-   m is 0, or 1, and n is 1, or 2, if M is Pd, or Pt,-   m is 0, 1, or 2, and n is 1, 2, or 3, if M is Rh, Ir or Re, and-   R²⁹; R²⁹; R^(25′) and R^(26′) are as defined in claim 1,-   with the proviso that at least one of R³, R⁸, R⁴ and R⁷ is different    from H. More preferably R³ and R⁸, or R⁴ and R⁷ are different from    H, most preferably R⁴ and R⁷ are different from H.

In a preferred embodiment the present invention is directed to compoundshaving a structure (Va), (Vb), (Vc), (VIa), (VIb), or (VIc) below:

wherein

-   R¹, R^(1′) and R² are independently of each other H, C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, which can optionally be substituted by one to    three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted    by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    or CN,-   R³, R⁸, R^(3′) and R^(8′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,    C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by E    and/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, or —NR²⁵R²⁶;-   R⁴, R⁷, R^(4′) and R^(7′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,    C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    C₂-C₁₈alkenyl, C₁-C₁₈alkoxy which is substituted by E and/or    interrupted by —O—, C₇-C₂₅arylalkyl, CN, —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl    which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl,    or C₁-C₁₈alkyl which is interrupted by —O—; or-   R²⁵ and R²⁶ together with the nitrogen atom to which they are bonded    form a heteroaromatic ring system

-    m′ is 0, 1, or 2;-   m″ can be the same or different at each occurence and is 0, 1, 2, or    3, especially 0, 1, or 2, very especially 0 or 1;-   R⁴¹ can be the same or different at each occurence and is Cl, F, CN,    N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a    C₁-C₂₅alkoxy group, in which one or more carbon atoms which are not    in neighbourhood to each other could be replaced by —NR⁴⁵—, —O—,    —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be    replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein    one or more carbon atoms can be replaced by O, S, or N, and/or which    can be substituted by one or more non-aromatic groups R⁴¹, or two or    more groups R⁴¹ form a ring system;-   R⁴⁵ is H, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, in which    one or more carbon atoms which are not in neighbourhood to each    other could be replaced by —NR^(45″)—, —O—, —S—, —C(═O)—O—, or,    —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be    replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein    one or more carbon atoms can be replaced by O, S, or N, and/or which    can be substituted by one or more non-aromatic groups R⁴¹, and-   R^(45″) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group,-   E is —OR²⁹; —SR²⁹; —NR^(25′)R^(26′), CN, or F; G is E, CF₃,    C₁-C₁₈alkyl, or C₂-C₁₈alkenyl,-   R²⁹; R²⁹; R^(25′) and R^(26′) are as defined in claim 1,-   M² is Rh, or Re, especially Ir,-   L is a bidentate ligand, and-   L′″ is a monodentate ligand, or-   a compound of claim 1 having a structure (VIIa), (VIIb), (VIIIa), or    (VIIIb) below:

-   wherein M⁴ is Pd, or Pt, and L, R¹, R², R^(1′), R³, R⁴, R^(3′),    R^(4′), R⁷, R⁸, R^(7′) and R^(8′) are as defined above.-   R² is H,-   R¹ and R^(1′) H, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, which can optionally    be substituted by one to three C₁-C₄alkyl groups, C₆-C₂₄aryl,    C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,    C₂-C₂₀heteroaryl which is substituted by G,

-    or CN,-   R³, R⁸, R^(3′) and R^(8′) are independently of each other H,    C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or    interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by    C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkoxy which are    interrupted by —O—; C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is    interrupted by —O—; or —NR²⁵R²⁶;-   R⁴, R⁷, R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl, or    C₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkoxy which are interrupted by    —O—; C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is interrupted by —O—; or    —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other; C₆-C₁₈aryl; C₆-C₁₈aryl    which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl,    or C₁-C₁₈alkoxy which are interrupted by —O—; or-   R²⁵ and R²⁶ together with the nitrogen atom to which they are bonded    form a heteroaromatic ring system

-    wherein G, R⁴¹ and m are as defined above;-   M⁴ is Pd, especially Pt,-   M² is Ir, and-   L is a bidentate ligand.

Monodentate ligands are preferably monoanionic. Such ligands can have Oor S as coordinating atoms, with coordinating groups such as alkoxide,carboxylate, thiocarboxylate, dithiocarboxylate, sulfonate, thiolate,carbamate, dithiocarbamate, thiocarbazone anions, sulfonamide anions,and the like. In some cases, ligands such as β-enolates can act asmonodentate ligands. The monodentate ligand can also be a coordinatinganion such as halide, nitrate, sulfate, hexahaloantimonate, and thelike. Examples of suitable monodentate ligands are shown below:

The monodentate ligands are generally available commercially.

In a preferred embodiment of the present invention the ligand is a(monoanionic) bidentate ligand. In general these ligands have N, O, P,or S as coordinating atoms and form 5- or 6-membered rings whencoordinated to the iridium. Suitable coordinating groups include amino,imino, amido, alkoxide, carboxylate, phosphino, thiolate, and the like.Examples of suitable parent compounds for these ligands includeβ-dicarbonyls (β-enolate ligands), and their N and S analogs; aminocarboxylic acids (aminocarboxylate ligands); pyridine carboxylic acids(iminocarboxylate ligands); salicylic acid derivatives (salicylateligands); hydroxyquinolines (hydroxyquinolinate ligands) and their Sanalogs; and diarylphosphinoalkanols (diarylphosphinoalkoxide ligands).

Examples of such bidentate ligands L are

wherein

-   R¹¹ and R¹⁵ are independently of each other hydrogen, C₁-C₈alkyl,    C₆-C₁₈aryl, C₂-C₁₀heteroaryl, or C₁-C₈ perfluoroalkyl,-   R¹² and R¹⁶ are independently of each other hydrogen, C₆-C₁₈aryl, or    C₁-C₈alkyl, and-   R¹³ and R¹⁷ are independently of each other hydrogen, C₁-C₈alkyl,    C₆-C₁₈aryl, C₂-C₁₀heteroaryl, C₁-C₈ perfluoroalkyl, or C₁-C₈alkoxy,    and-   R¹⁴ is C₁-C₈alkyl, C₆-C₁₀aryl, or C₇-C₁₁aralkyl,-   R¹⁸ is C₆-C₁₀aryl,-   R¹⁹ is C₁-C₈alkyl, C₁-C₈ perfluoroalkyl,-   R²⁰ is C₁-C₈alkyl, or C₆-C₁₀aryl,-   R²¹ is hydrogen, C₁-C₈alkyl, or C₁-C₈alkoxy, which may be partially    or fully fluorinated,-   R²² and R²³ are independently of each other C_(q)(H+F)_(2q+1), or    C₆(H+F)_(5,) R²⁴ can be the same or different at each occurrence and    is selected from H, or C_(q)(H+F)_(2q+1),-   q is an integer of 1 to 24, p is 2, or 3, and-   R⁴⁶ is C₁-C₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted    by C₁-C₈alkyl.

Examples of suitable phosphino alkoxide ligands

are listed below:

-   3-(diphenylphosphino)-1-oxypropane [dppO]-   1,1-bis(trifluoromethyl)-2-(diphenylphosphino)-ethoxide [tfmdpeO].

Examples of particularly suitable compounds HL,

from which the ligands L are derived, include

(2,4-pentanedionate [acac]),

(2,2,6,6-tetramethyl-3,5-heptanedionate [TMH]),

(1,3-diphenyl-1,3-propanedionate [DI]),

(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate [TTFA]),

(7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedionate [FOD]),

(1,1,1,3,5,5,5-heptafluoro-2,4-pentanedionate [F7acac]),

(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate [F6acac]),

(1-phenyl-3-methyl-4-i-butyryl-pyrazolinonate [FMBP]),

The hydroxyquinoline parent compounds, HL, can be substituted withgroups such as alkyl or alkoxy groups which may be partially or fullyfluorinated. In general, these compounds are commercially available.Examples of suitable hydroxyquinolinate ligands, L, include:

-   8-hydroxyquinolinate [8hq]-   2-methyl-8-hydroxyquinolinate [Me-8hq]-   10-hydroxybenzoquinolinate [10-hbq]

In a further embodiment of the present invention the bidentate ligand Lis a ligand of formula

wherein the ring A,

represents an optionally substituted aryl group which can optionallycontain heteroatoms, the ring B,

represents an optionally substituted nitrogen containing aryl group,which can optionally contain further heteroatoms, or the ring A may betaken with the ring B binding to the ring A to form a ring.

The preferred ring A includes a phenyl group, a substituted phenylgroup, a naphthyl group, a substituted naphthyl group, a furyl group, asubstituted furyl group, a benzofuryl group, a substituted benzofurylgroup, a thienyl group, a substituted thienyl group, a benzothienylgroup, a substituted benzothienyl group, and the like. The substitutenton the substituted phenyl group, substituted naphthyl group, substitutedfuryl group, substituted benzofuryl group, substituted thienyl group,and substituted benzothienyl group include C₁-C₂₄alkyl groups,C₂-C₂₄alkenyl groups, C₂-C₂₄alkynyl groups, aryl groups, heteroarylgroups, C₁-C₂₄alkoxy groups, C₁-C₂₄alkylthio groups, a cyano group,C₂-C₂₄acyl groups, C₁-C₂₄alkyloxycarbonyl groups, a nitro group, halogenatoms, alkylenedioxy groups, and the like.

In said embodiment the bidentate ligand

is preferably a group of formula

wherein R²¹¹, R²¹², R²¹³, and R²¹⁴ are independently of each otherhydrogen, C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, aryl, heteroaryl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, cyano, acyl, alkyloxycarbonyl, a nitrogroup, or a halogen atom; the ring A represents an optionallysubstituted aryl or heteroaryl group; or the ring A may be taken withthe pyridyl group binding to the ring A to form a ring; the alkyl group,alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxygroup, alkylthio group, acyl group, and alkyloxycarbonyl grouprepresented by R²¹¹, R²¹², R²¹³, and R²¹⁴ may be substituted; or R²¹³and R²¹⁴ or R²¹² and R²¹³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are as defined above.

Examples of preferred classes of such bidentate ligands L are compoundsof the formula

especially

wherein Y is S, O, NR²⁰⁰, wherein R²⁰⁰ is C₁-C₄alkyl, C₂-C₄alkenyl,optionally substituted C₆-C₁₀aryl, especially phenyl, —(CH₂)_(r)—Ar,wherein Ar is an optionally substituted C₆-C₁₀aryl, especially

a group —(CH₂)_(r′)X²⁰, wherein r′ is an integer of 1 to 5, X²⁰ ishalogen, especially F, or Cl; hydroxy, cyano, —O—C₁-C₄alkyl,di(C₁-C₄alkyl)amino, amino, or cyano; a group—(CH₂)_(r)—OC(O)(CH₂)_(r″)CH₃, wherein r is 1, or 2, and r″ is 0, or 1;

—NH-Ph, —C(O)CH₃, —CH₂—O—(CH₂)₂—Si(CH₃)₃, or

Another preferred class of ligands L is described in WO06/000544, ofwhich the following can advantageously be used according to the presentinvention:

wherein

-   Q¹ and Q² are independently of each other hydrogen, C₁-C₂₄alkyl, or    C₆-C₁₈aryl, A^(21′) is hydrogen,-   A^(22′) is hydrogen, or C₆-C₁₀aryl,-   A^(23′) is hydrogen, or C₆-C₁₀aryl,-   A^(24′) is hydrogen, or-   A^(23′) and A^(24′), or A^(23′) and A^(24′) together form a group

-    wherein R^(205′), R^(206′), R^(207′) and R^(208′) are independently    of each other H, or C₁-C₈alkyl,-   R^(42′) is H, F, C₁-C₄alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl,-   R^(43′) is H, F, C₁-C₄alkyl, C₁-C₈alkoxy, C₁-C₄ perfluoroalkyl, or    C₆-C₁₀aryl,-   R^(44′) is H, F, C₁-C₄alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl,    and-   R^(45′) is H, F, C₁-C₄alkyl, C₁-C₈alkoxy, or C₁-C₄ perfluoroalkyl.

Another preferred class of bidentate ligands L is a compound of formula

wherein R²¹⁴ is hydrogen, halogen, especially F, or Cl; C₁-C₄alkyl,C₁-C₄perfluoroalkyl, C₁-C₄alkoxy, or optionally substituted C₆-C₁₀aryl,especially phenyl,

-   R²¹⁵ is hydrogen, halogen, especially F, or Cl; C₁-C₄alkyl, C₁-C₄    perfluoroalkyl, optionally substituted C₆-C₁₀aryl, especially    phenyl, or optionally substituted C₆-C₁₀ perfluoroaryl, especially    C₆F₅,-   R²¹⁶ is hydrogen, C₁-C₄alkyl, C₁-C₄ perfluoroalkyl, optionally    substituted C₆-C₁₀aryl, especially phenyl, or optionally substituted    C₆-C₁₀ perfluoroaryl, especially C₆F₅,-   R²¹⁷ is hydrogen, halogen, especially F, or Cl; nitro, cyano,    C₁-C₄alkyl, C₁-C₄ perfluoroalkyl, C₁-C₄alkoxy, or optionally    substituted C₆-C₁₀aryl, especially phenyl,-   R²¹⁰ is hydrogen,-   R²¹¹ is hydrogen, halogen, especially F, or Cl; nitro, cyano,    C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkenyl, C₁-C₄ perfluoroalkyl,    —O—C₁-C₄ perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, especially    tri(methyl)silanyl, optionally substituted C₆-C₁₀aryl, especially    phenyl, or optionally substituted C₆-C₁₀ perfluoroaryl, especially    C₆F₅,-   R²¹² is hydrogen, halogen, especially F, or Cl; nitro, hydroxy,    mercapto, amino, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄ perfluoroalkyl,    C₁-C₄alkoxy, —O—C₁-C₄ perfluoroalkyl, —S—C₁-C₄alkyl,    tri(C₁-C₄alkyl)siloxanyl, optionally substituted —O—C₆-C₁₀aryl,    especially phenoxy, cyclohexyl, optionally substituted C₆-C₁₀aryl,    especially phenyl, or optionally substituted C₆-C₁₀perfluoroaryl,    especially C₆F₅, and-   R²¹³ is hydrogen, nitro, cyano, C₁-C₄alkyl, C₂-C₄alkenyl, C₁-C₄    perfluoroalkyl, —O—C₁-C₄perfluoroalkyl, tri(C₁-C₄alkyl)silanyl, or    optionally substituted C₆-C₁₀aryl, especially phenyl.

Specific examples of bidentate ligands L are the following compounds(X-1) to (X-57):

In case of the metal complex (L^(a))₂IrL′ three isomers can exist.

In some cases mixtures of isomers are obtained. Often the mixture can beused without isolating the individual isomers. The isomers can beseparated by conventional methods, as described in A. B. Tamayo et al.,J. Am. Chem. Soc. 2003, 125, 7377-7387.

The at present most preferred ligands L are listed below:

In a preferred embodiment the present invention is directed to compoundsof formula Va, or Vb, wherein M² is Rh, or Re, especially Ir,

-   R¹ and R² are independently of each other H, C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, which can optionally be substituted by one to    three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted    by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    or CN, or R¹ and R² together form a group

-    R^(206′), R^(208′), R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹ and R²¹⁰ are    independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, or    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl or    C₁-C₁₈alkoxy; R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁷ and R³⁰⁸ are    independently of each other H, or C₁-C₁₈alkyl, R³, R⁸, R^(3′) and    R^(8′) are independently of each other H, C₆-C₂₄aryl, C₆-C₂₄aryl    which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which    is substituted by G, C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which    is substituted by E and/or interrupted by —O—, C₇-C₂₅arylalkyl, CN,    or —NR²⁵R²⁶;-   R⁴ and R⁷ are independently of each other H, C₆-C₂₄aryl, C₆-C₂₄aryl    which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which    is substituted by G, C₂-C₁₈alkenyl, C₁-C₁₈alkoxy which is    substituted by E and/or interrupted by —O—, C₇-C₂₅arylalkyl, CN,    —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl    which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl;    or C₁-C₁₈alkyl which is interrupted by —O—;-   E is —OR²⁹; —SR²⁹; —NR^(25′)R^(26′), —CF₃, —CN, F; G is E,    C₁-C₁₈alkyl, or C₂-C₁₈alkenyl, and L is a bidentate ligand.

In a particularly preferred embodiment R¹ is H, C₁-C₁₀alkyl, cyclohexyl,which can optionally be substituted by one to three C₁-C₄alkyl groups,phenyl, which may be substituted one to five times by F, such as

CF₃, such as

such as

and R² is H, CH₃.

In said embodiment compounds are even more preferred, wherein R⁴ and R⁷are independently of each other H, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₁-C₁₈alkoxy which may be interrupted by —O—, or—NR²⁵R²⁶.

In said embodiment the compounds of formula

are most preferred, wherein M² is Ir,

-   R¹ is H, C₁-C₁₈alkyl, cyclohexyl, which can optionally be    substituted by one to three C₁-C₄alkyl groups,

-    wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, especially 0, 1,    2, or 5, R¹¹ can be same, or different in each occurrence and is    C₁-C₂₅alkyl, C₁-C₂₅alkoxy, —NR²⁵R²⁶, F, or CF₃,-   R² is H, or CH₃,-   R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy which    may be interrupted by —O—, or —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other

-    R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which    may optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and    R²⁶ together with the nitrogen atom to which they are bonded form a    group of formula

-    R⁴¹ is H, C₁-C₂₅alkyl, and-   L is

In another preferred embodiment the present invention is directed tocompounds of formula VIIIa, or VIIb, wherein M⁴ is Pd, especially Pt,

-   R¹ and R² are independently of each other H, C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, which can optionally be substituted by one to    three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted    by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,    or CN, or R¹ and R² together form a group

-   R^(206′), R^(208′), R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹ and R²¹⁰ are    independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, or    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl or    C₁-C₁₈alkoxy;-   R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁷ and R³⁰⁸ are independently    of each other H, or C₁-C₁₈alkyl, R³, R⁸, R^(3′) and R^(8′) are    independently of each other H, C₆-C₂₄aryl, C₆-C₂₄aryl which is    substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is    substituted by G, C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is    substituted by E and/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, or    —NR²⁵R²⁶;-   R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,    C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,    C₁-C₁₈alkoxy which is substituted by E and/or interrupted by —O—,    C₇-C₂₅arylalkyl, CN, —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl; C₆-C₁₈aryl    which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl;    or C₁-C₁₈alkyl which is interrupted by —O—;-   E is —OR²⁹; —SR²⁹; —NR^(25′)R^(26′); G is E, C₁-C₁₈alkyl, or    C₂-C₁₈alkenyl, and L is a bidentate ligand.

In said embodiment compounds are even more preferred, wherein R⁴ and R⁷are independently of each other H, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₁-C₁₈alkoxy which may be interrupted by —O—, or—NR²⁵R²⁶.

In said embodiment the compounds of formula

are even more preferred, wherein M⁴ is Pt,

-   R¹ is H, C₁-C₁₈alkyl, cyclohexyl, which can optionally be    substituted by one to three C₁-C₄alkyl groups,

-    wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, especially 0, 1,    2, or 5, R¹¹ can be same, or different in each occurrence and is    C₁-C₂₅alkyl, C₁-C₂₅alkoxy, or NR²⁵R²⁶, F, or CF₃,-   R² is H,-   R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy which    may be interrupted by —O—, or —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other

-    R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which    may optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and    R²⁶ together with the nitrogen atom to which they are bonded form a    group of formula

-    R⁴¹ is H, or C₁-C₂₅alkyl, and-   L is

Preferences for the bidentate ligand L are given above, wherein thefollowing ligands L are advantageously used:

Higher preference is given to

Even higher preference is given to

The metal complexes of the present invention are preferably non-ionic(uncharged).

If R¹ and R² together form a ring, they are preferably a group

wherein R³⁰¹, R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁷ and R³⁰⁸ areindependently of each other H, or C₁-C₈alkyl, especially H.

Compounds are preferred, wherein at least one of the substituents R¹, R⁴and R⁷ (especially R¹, R⁴ or R⁷; or R⁴ or R⁷) is a functional grouphaving charge transport properties, in particular hole transportproperties. Examples of substituents having hole transport propertiesare —NR²⁵R²⁶, or C₆-C₂₄aryl, such as phenyl, 1-, or 2-naphthyl, which issubstituted by —NR²⁵R²⁶, wherein R²⁵ and R²⁶ are as defined above, andare preferably independently of each other

wherein R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, whichmay optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and R²⁶together with the nitrogen atom to which they are bonded form a group offormula

R⁴¹ is H, or C₁-C₂₅alkyl.

In a particularly preferred embodiment the present invention is directedto compounds of formula

wherein M² is iridium, R¹ is H, cyclohexyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups, C₁-C₁₈alkyl,

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, especially 0, 1, 2, or5, R¹¹ can be same, or different in each occurrence and is C₁-C₂₅alkyl,C₁-C₂₅alkoxy, —NR²⁵R²⁶, F, or CF₃,

-   R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy,    which may be interrupted by —O—, or —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other

-    R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which    may optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and    R²⁶ together with the nitrogen atom to which they are bonded form a    group of formula

-    R⁴¹ is H, or C₁-C₂₅alkyl, and L is as defined above. In said    embodiment compounds are more preferred, wherein R¹ is H,    C₁-C₁₈alkyl,

-    and R⁴ and R⁷ are independently of each other H, C₆-C₂₄aryl,    C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy, which may be    interrupted by —O—, or —NR²⁵R²⁶. In said embodiment compounds of    formula

-    wherein R¹ is H, C₁-C₁₈alkyl,

-    and R⁴ and R⁷ are independently of each other phenyl, 1-, or    2-naphthyl, which is substituted by —NR²⁵R²⁶; or —NR²⁵R²⁶, are even    more preferred.

If a mixture of two isomers of mono-substituted dibenzoquinoxalineligands

in which R¹ is, for example, H, CH₃, 2-ethylhexyl, cyclohexyl, which canoptionally be substituted by one to three C₁-C₄alkyl groups, or phenyl,and R⁴ is, for example, a substituted phenyl, is employed, said isomerscoordinate in two ways to iridium, i.e.

and isomers of iridium complexes are obtained.

In a particularly preferred embodiment the present invention is directedto compounds of formula LIr(L^(a))₂, or Ir(L^(a))₃, wherein L^(a) is agroup of formula

wherein R¹ is H, C₁-C₁₈alkyl, cyclohexyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups,

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, especially 0, 1, 2, or5, R¹¹ can be same, or different in each occurrence and is C₁-C₂₅alkyl,C₁-C₂₅alkoxy, —NR²⁵R²⁶, F, or CF₃,

-   R² is H, or CH₃,-   R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,    C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by —NR²⁵R²⁶,    C₁-C₁₈alkoxy which may be interrupted by —O—, or —NR²⁵R²⁶;-   R²⁵ and R²⁶ are independently of each other

-    and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which may    optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and R²⁶    together with the nitrogen atom to which they are bonded form a    group of formula

-    R⁴¹ is H, or C₁-C₂₅alkyl, and L is as defined above. In said    embodiment ligands L^(a) are even more preferred, wherein R¹ is H,    C₁-C₁₈alkyl,

-    R² is H, or CH₃, and R⁴ and R⁷ are independently of each other H,    C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy,    which may be interrupted by —O—, or —NR²⁵R²⁶. In said embodiment    ligands L^(a) are even more preferred, wherein R¹ is C₁-C₁₈alkyl, R²    is H, or CH₃, and R⁴ and R⁷ are independently of each other

-    or R¹ is

-    and R⁴ and R⁷ are independently of each other

-    or R¹ is H, C₁-C₁₈alkyl,

-    and R⁴ and R⁷ are independently of each other phenyl, which is    substituted by —NR²⁵R²⁶; or —NR²⁵R²⁶. In said embodiment ligands    L^(a) are even more preferred wherein R² is H.

In a particularly preferred embodiment the present invention is directedto compounds of formula

wherein M² is iridium, R¹ is NR²⁵R²⁶, or

R¹¹ is —NR²⁵R²⁶, R²⁵, R²⁶ and L are as defined above.

In a particularly preferred embodiment the present invention is directedto compounds of formula

wherein M² is iridium, R¹ is H, C₁-C₁₈alkyl, cyclohexyl, which canoptionally be substituted by one to three C₁-C₄alkyl groups,

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, especially 0, 1, 2, or5, R¹¹ can be same, or different in each occurrence and is C₁-C₂₅alkyl,C₁-C₂₅alkoxy, —NR²⁵R²⁶, F, or CF₃,

-   R⁴ and R⁷ are independently of each other —SR²⁹, wherein R²⁹ is    C₁-C₁₈alkyl, and R²⁵, R²⁶ and L are as defined above.

A compound of formula Vb, wherein R¹ is phenyl, and R², R³, R⁴, R⁷ andR⁸ are H is not comprised by the present invention.

In a particularly preferred embodiment the present invention is directedto compounds of formula

wherein R¹ is C₂-C₁₀alkyl, such as methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, 2-ethylhexyl, cyclohexyl, which can optionallybe substituted by one to three C₁-C₄alkyl groups, R² is H, or CH₃, and Lis

In said embodiment compounds of formula

are even more preferred, wherein L is

In said embodiment compounds of formula

are even more preferred, wherein R² is H. Said compounds are very wellvaporizable and are characterized by an excellent thermal stability andvaporizability, and high efficiency.

Examples of specific compounds of formula Va are compounds A-1 to A-176,compounds B-1 to B-176, C-1 to C-95, compounds D-1 to D-95 and compoundsE-1 to E-36 (see claim 6). Special emphasis among them is given tocompounds A-1 to A-4, A-17 to A-22, A-35 to A-40, A-53 to A-58, A-71 toA-76, A-89 to A-94, A-107 to A-112, A-125 to A-130, A-143 to A-151,A-163 to A-165, A-167 to A-172, and A-174 to A-176; and B-1 to B-4, B-17to B-22, B-35 to B-40, B-53 to B-58, B-71 to B-76, B-89 to B-94, B-107to B-112, B-125 to B-130, B-143 to B-151, B-156, B-163 to B-165, B-167to B-172, and B-174 to B-176; and C-1, C-2, C-9 to C-12, C-19 to C-21,C-28 to C-30, C-37 to C-39, C-46 to C-48, C-55 to C-57, C-64 to C-66,C-70 to C-79, C82 to C-84, C-86 to C-91, and C-93 to C-95; and D-1, D-2,D-9 to D-12, D-19 to D-21, D-28 to D-30, D-37 to D-39, D-46 to D-48,D-55 to D-57, D-64 to D-66, D-70 to D-84, D-86 to D-91, and D-93 toD-95; and E-1 to E-6, E-10 to E-15, and E-28 to E-33. More preferredcompounds are A-1, A-19, A-37, A-55, A-73, A-91, A-109, A-127, A-143,A-145, A-147, A-149, and A-151; and B-1, B-19, B-37, B-55, B-73, B-91,B-109, B-127, B-143, B-145, B-147, B-149, B-151, B-156, B-163 to B-165,B-167 to B-172, and B-174 to B-176; and C-1, C-10, C-20, C-29, C-37,C-38, C-46, C-47, C-56, C-64, C-65, and C-73 to C-79; and D-1, D-9,D-10, D-19, D-20, D-28, D-29, D-37, D-38, D-46, D-47, D-55, D-56, D-64,D-65, and D-73 to D-95; and E-1, E-5, E-6, E-10, E-14, E-15, E-19, E-23,E-24, E-28, E-32, and E-33. Most preferred are compounds A-1, B-1, C-1,D-1, C-79, D-79, C-81, D-81, A-151 and B-151.

The metal complexes of the present invention can be prepared accordingto usual methods known in the prior art. A convenient one-step methodfor preparing iridium metal complexes of formula Ir(L^(a))₃

comprises reacting commercially available iridium trichloride hydratewith an excess of L^(a)H in the presence of 3 equivalents silvertrifluoroacetate and optionally in the presence of a solvent (such ashalogen based solvents, alcohol based solvents, ether based solvents,ester based solvents, ketone based solvents, nitrile based solvents, andwater). The tris-cyclometalated iridium complexes are isolated andpurified by conventional methods. In some cases mixtures of isomers areobtained. Often the mixture can be used without isolating the individualisomers. The iridium metal complexes of formula Ir(L^(a))₂L can, forexample, be prepared by first preparing an intermediate iridium dimer offormula

wherein X is H, methyl, or ethyl, and L^(a) is as defined above, andthen addition of HL. The iridium dimers can generally be prepared byfirst reacting iridium trichloride hydrate with HL^(a) and adding NaXand by reacting iridium trichloride hydrate with HL^(a) in a suitablesolvent, such as 2-ethoxyethanol. The compounds of formula

are new and form a further aspect of the present invention.

Accordingly, the present invention relates to compounds of formula

wherein X is H, methyl, or ethyl, and L^(a)is

is wherein R¹, R², R^(1′), R³, R⁴, R^(3′), R^(4′), R⁵, R⁶, R^(5′),R^(6′), R⁷, R⁸, R^(7′) and R^(8′) are as defined above, with the provisothat at least one of R¹, R², R³, R⁸, R⁴, R⁷, R⁸ and R⁶ is different fromH and the further proviso that a compound of formula

wherein L^(a) is

a compound of formula

wherein L^(a) is

and a compound of formula

wherein L^(a) is

are excluded.

Compounds of formula VIIIa, or VIIb can be synthesized, for example, asoutlined in FIGS. 7 and 8 of U.S. Pat. No. 7,166,368.

Halogen is fluorine, chlorine, bromine and iodine.

C₁-C₂₄alkyl is a branched or unbranched radical such as for examplemethyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,icosyl or docosyl.

C₁-C₂₄ perfluoroalkyl is a branched or unbranched radical such as forexample —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF(CF₃)₂, —(CF₂)₃CF₃, and —C(CF₃)₃.

C₁-C₂₄alkoxy radicals are straight-chain or branched alkoxy radicals,e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy,isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy,pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy.

C₂-C₂₄alkenyl radicals are straight-chain or branched alkenyl radicals,such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl,isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂₋₂₄alkynyl is straight-chain or branched and preferably C₂₋₈alkynyl,which may be unsubstituted or substituted, such as, for example,ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl,2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl,1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl,trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl,1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

C₄-C₁₈cycloalkyl, especially C₅-C₁₂cycloalkyl, is preferablyC₅-C₁₂cycloalkyl or said cycloalkyl substituted by one to threeC₁-C₄alkyl groups, such as, for example, cyclopentyl, methylcyclopentyl,dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl,trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl, 1-adamantyl, or 2-adamantyl.Cyclohexyl, 1-adamantyl and cyclopentyl are most preferred.

Examples of C₄-C₁₈cycloalkyl, which is interrupted by S, O, or NR²⁵, arepiperidyl, piperazinyl and morpholinyl.

C₂-C₂₄alkenyl is for example vinyl, allyl, butenyl, pentenyl, hexenyl,heptenyl, or octenyl.

Aryl is usually C₆-C₃₀aryl, preferably C₆-C₂₄aryl, which optionally canbe substituted, such as, for example, phenyl, 4-methylphenyl,4-methoxyphenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl,anthryl, tetracyl, pentacyl, hexacyl, terphenylyl or quadphenylyl; orphenyl substituted by one to three C₁-C₄alkyl groups, for example o-, m-or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

C₇-C₂₄aralkyl radicals are preferably C₇-C₁₅aralkyl radicals, which maybe substituted, such as, for example, benzyl, 2-benzyl-2-propyl,β-phenethyl, α-methylbenzyl, α,α-dimethylbenzyl, ω-phenyl-butyl,ω-phenyl-octyl, ω-phenyl-dodecyl; or phenyl-C₁-C₄alkyl substituted onthe phenyl ring by one to three C₁-C₄alkyl groups, such as, for example,2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl,2,6-dimethylbenzyl or 4-tert-butylbenzyl. or3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.

Heteroaryl is typically C₂₋C₂₆heteroaryl, i.e. a ring with five to sevenring atoms or a condensed rig system, wherein nitrogen, oxygen or sulfurare the possible hetero atoms, and is typically an unsaturatedheterocyclic radical with five to 30 atoms having at least sixconjugated π-electrons such as thienyl, benzo[b]thienyl,dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl,benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl,imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl,pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl,purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl,naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl,carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl,acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can beunsubstituted or substituted.

C₆-C₁₈cycloalkoxy is, for example, cyclopentyloxy, cyclohexyloxy,cycloheptyloxy or cyclooctyloxy, or said cycloalkoxy substituted by oneto three C₁-C₄alkyl, for example, methylcyclopentyloxy,dimethylcyclopentyloxy, methylcyclohexyloxy, dimethylcyclohexyloxy,trimethylcyclohexyloxy, or tert-butylcyclohexyloxy.

C₆-C₂₄aryloxy is typically phenoxy or phenoxy substituted by one tothree C₁-C₄alkyl groups, such as, for example o-, m- or p-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or2,6-diethylphenoxy.

C₆-C₂₄aralkoxy is typically phenyl-C₁-C₉alkoxy, such as, for example,benzyloxy, α-methylbenzyloxy, α,α-dimethylbenzyloxy or 2-phenylethoxy.

C₁-C₂₄alkylthio radicals are straight-chain or branched alkylthioradicals, such as e.g. methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio,heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio oroctadecylthio. C₁-C₂₄alkylselenium and C₁-C₂₄alkyltellurium areC₁-C₂₄alkylSe— and C₁-C₂₄alkylTe—, respectively.

Examples of a five or six membered ring formed by R⁹ and R¹⁰ and R²⁵ andR²⁶, respectively are heterocycloalkanes or heterocycloalkenes havingfrom 3 to 5 carbon atoms which can have one additional hetero atomselected from nitrogen, oxygen and sulfur, for example

which can be part of a bicyclic system, for example

Possible substituents of the above-mentioned groups are C₁-C₈alkyl, ahydroxyl group, a mercapto group, C₁-C₈alkoxy, C₁-C₈alkylthio, halogen,especially fluorine, halo-C₁-C₈alkyl, especially fluoro-C₁-C₈alkyl, acyano group, an aldehyde group, a ketone group, a carboxyl group, anester group, a carbamoyl group, an amino group, a nitro group or a silylgroup.

The term “haloalkyl” means groups given by partially or whollysubstituting the above-mentioned alkyl group with halogen, such astrifluoromethyl etc. The term “silyl group” means a group of formula—SiR^(105′)R^(106′)R^(107′), wherein R^(105′), R^(106′) and R^(107′) areindependently of each other a C₁-C₈alkyl group, in particular a C₁-C₄alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as atrimethylsilyl group.

If a substituent, such as, for example, R⁴¹, occurs more than one timein a group, it can be different in each occurrence.

The present invention is also directed to an electronic devicecomprising the metal complex and its fabrication process. The electronicdevice can comprise at least one organic active material positionedbetween two electrical contact layers, wherein at least one of thelayers of the device includes the metallic complex compound. Theelectronic device can comprise an anode layer (a), a cathode layer (e),and an active layer (c). Adjacent to the anode layer (a) is an optionalhole-injecting/transport layer (b), and adjacent to the cathode layer(e) is an optional electron-injection/transport layer (d). Layers (b)and (d) are examples of charge transport layers.

The active layer (c) can comprise at least approximately 1 weightpercent of metal complex previously described.

In some embodiments, the active layer (c) may be substantially 100% ofthe metal complex because a host charge transporting material, such asAlq₃ is not needed. By “substantially 100%” it is meant that the metalcomplex is the only material in the layer, with the possible exceptionof impurities or adventitious by-products from the process to form thelayer. Still, in some embodiments, the metal complex may be a dopantwithin a host material, which is typically used to aid charge transportwithin the active layer (c). The active layer (c), including any of themetal complexes, can be a small molecule active material.

The device may include a support or substrate (not shown) adjacent tothe anode layer (a) or the cathode layer (e). Most frequently, thesupport is adjacent the anode layer (a). The support can be flexible orrigid, organic or inorganic. Generally, glass or flexible organic filmsare used as a support. The anode layer (a) is an electrode that is moreefficient for injecting holes compared to the cathode layer (e). Theanode can include materials containing a metal, mixed metal, alloy,metal oxide or mixed-metal oxide. Suitable metal elements within theanode layer (a) can include the Groups 4, 5, 6, and 8-11 transitionmetals. If the anode layer (a) is to be light transmitting, mixed-metaloxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, may beused. Some non-limiting, specific examples of materials for anode layer(a) include indium-tin-oxide (“ITO”), aluminum-tin-oxide, gold, silver,copper, nickel, and selenium.

The anode layer (a) may be formed by a chemical or physical vapordeposition process or spin-cast process. Chemical vapor deposition maybe performed as a plasma-enhanced chemical vapor deposition (“PECVD”) ormetal organic chemical vapor deposition (“MOCVD”).

Physical vapor deposition can include all forms of sputtering (e.g., ionbeam sputtering), e-beam evaporation, and resistance evaporation.

Specific forms of physical vapor deposition include rf magnetronsputtering or inductively-coupled plasma physical vapor deposition(“ICP-PVD”). These deposition techniques are well-known within thesemiconductor fabrication arts.

A hole-transport layer (b) may be adjacent the anode. Both holetransporting small molecule compounds and polymers can be used.

Commonly used hole transporting molecules, in addition toN,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD) andbis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP),include: polyvinyl-carbazol, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane(TAPC);N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);a-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB);N,N′-di-α-naphthyl-N,N′-diphenyl-4,4′-diphenyldiamine (-NPD), andporphyrinic compounds, such as copper phthalocyanine.

Commonly used hole transporting polymers are polyvinylcarbazole,(phenylmethyl) polysilane, poly(3,4-ethylendioxythiophene) (PEDOT), andpolyaniline. Hole-transporting polymers can be obtained by dopinghole-transporting molecules such as those mentioned above into polymerssuch as polystyrene and polycarbonate.

The hole-injection/transport layer (b) can be formed using anyconventional means, including spin-coating, casting, and printing, suchas gravure printing. The layer can also be applied by ink jet printing,thermal patterning, or chemical, or physical vapor deposition.

Usually, the anode layer (a) and the hole-injection/transport layer (b)are patterned during the same lithographic operation. The pattern mayvary as desired. The layers can be formed in a pattern by, for example,positioning a patterned mask or resist on the first flexible compositebarrier structure prior to applying the first electrical contact layermaterial. Alternatively, the layers can be applied as an overall layer(also called blanket deposit) and subsequently patterned using, forexample, a patterned resist layer and wet-chemical or dry-etchingtechniques. Other processes for patterning that are well known in theart can also be used. When the electronic devices are located within anarray, the anode layer (a) and hole injection/transport layer (b)typically are formed into substantially parallel strips having lengthsthat extend in substantially the same direction.

The active layer (c) may comprise the metal complexes described herein.The particular material chosen may depend on the specific application,potentials used during operation, or other factors. The active layer (c)may comprise a host material capable of transporting electrons and/orholes, doped with an emissive material that may trap electrons, holes,and/or excitons, such that excitons relax from the emissive material viaa photoemissive mechanism. Active layer (c) may comprise a singlematerial that combines transport and emissive properties. Whether theemissive material is a dopant or a major constituent, the active layermay comprise other materials, such as dopants that tune the emission ofthe emissive material. Active layer (c) may include a plurality ofemissive materials capable of, in combination, emitting a desiredspectrum of light. Examples of phosphorescent emissive materials includethe metal complexes of the present invention. Examples of fluorescentemissive materials include DCM and DMQA. Examples of host materialsinclude Alq₃, BAlq, BAlq₂ (Appl. Phys. Lett. 89 (2006) 061111), CBP andmCP. Examples of emissive and host materials are disclosed in U.S. Pat.No. 6,303,238, which is incorporated by reference in its entirety.

The active layer (c) can be applied from solutions by any conventionaltechnique, including spin coating, casting, and printing. The activeorganic materials can be applied directly by vapor deposition processes,depending upon the nature of the materials.

Optional layer (d) can function both to facilitate electroninjection/transport, and also serve as a buffer layer or confinementlayer to prevent quenching reactions at layer interfaces. Morespecifically, layer (d) may promote electron mobility and reduce thelikelihood of a quenching reaction if layers (c) and (e) would otherwisebe in direct contact. Examples of materials for optional layer (d)include metal-cheated oxinoid compounds (e.g., Alq₃ or the like);phenanthroline-based compounds (e.g.,2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (“DDPA”),4,7-diphenyl-1,10-phenanthroline (“DPA”), or the like; azole compounds(e.g., 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (“PBD”) orthe like, 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole(“TAZ”) or the like; other similar compounds; or any one or morecombinations thereof. Alternatively, optional layer (d) may be inorganicand comprise BaO, LiF, Li₂O, or the like. Preferred electrontransportingmaterials are tris(8-hydroxyquinolato)aluminium (Alq₃),bis(2-methyl-8-hydroxyquinaolato)(p-phenylphenolato) aluminium (BAlq),tetrakis(8-hydroxyquinolato)zirconium (ZrQ) and mixtures thereof.

The electron injection/transport layer (d) can be formed using anyconventional means, including spin-coating, casting, and printing, suchas gravure printing. The layer can also be applied by ink jet printing,thermal patterning, or chemical or physical vapor deposition.

The cathode layer (e) is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode layer (e)can be any metal or nonmetal having a lower work function than the firstelectrical contact layer (in this case, the anode layer (a)). Materialsfor the second electrical contact layer can be selected from alkalimetals of Group 1 (e.g., Li, Na, K, Rb, Cs), the Group 2 (alkalineearth) metals, the Group 12 metals, the rare earths, the lanthanides(e.g., Ce, Sm, Eu, or the like), and the actinides. Materials, such asaluminum, indium, calcium, barium, yttrium, and magnesium, andcombinations thereof, may also be used. Li-containing organometalliccompounds, LiF, and Li₂O can also be deposited between the organic layerand the cathode layer to lower the operating voltage. Specificnon-limiting examples of materials for the cathode layer (e) includebarium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium,or samarium.

The cathode layer (e) is usually formed by a chemical or physical vapordeposition process. In general, the cathode layer will be patterned, asdiscussed above in reference to the anode layer (a) and optional holeinjecting layer (b). If the device lies within an array, the cathodelayer (e) may be patterned into substantially parallel strips, where thelengths of the cathode layer strips extend in substantially the samedirection and substantially perpendicular to the lengths of the anodelayer strips.

Electronic elements called pixels are formed at the cross points (wherean anode layer strip intersects a cathode layer strip when the array isseen from a plan or top view).

In other embodiments, additional layer (s) may be present within organicelectronic devices. For example, a layer (not shown) between the holeinjecting layer (b) and the active layer (c) may facilitate positivecharge transport, band-gap matching of the layers, function as aprotective layer, or the like. Similarly, additional layers (not shown)between the electron injecting layer (d) and the cathode layer (e) mayfacilitate negative charge transport, band-gap matching between thelayers, function as a protective layer, or the like. Layers that areknown in the art can be used. Some or all of the layers may be surfacetreated to increase charge carrier transport efficiency. The choice ofmaterials for each of the component layers may be determined bybalancing the goals of providing a device with high device efficiencywith the cost of manufacturing, manufacturing complexities, orpotentially other factors.

The charge transport layers (b) and (d) are generally of the same typeas the active layer (c). More specifically, if the active layer (c) hasa small molecule compound, then the charge transport layers (b) and (d),if either or both are present, can have a different small moleculecompound. If the active layer (c) has a polymer, the charge transportlayers (b) and (d), if either or both are present, can also have adifferent polymer. Still, the active layer (c) may be a small moleculecompound, and any of its adjacent charge transport layers may bepolymers.

Each functional layer may be made up of more than one layer. Forexample, the cathode layer may comprise a layer of a Group 1 metal and alayer of aluminum. The Group 1 metal may lie closer to the active layer(c), and the aluminum may help to protect the Group 1 metal fromenvironmental contaminants, such as water.

Although not meant to limit, the different layers may have the followingrange of thicknesses: inorganic anode layer (a), usually no greater thanapproximately 500 nm, for example, approximately 50-200 nm; optionalhole-injecting layer (b), usually no greater than approximately 100 nm,for example, approximately 50-200 nm; active layer (c), usually nogreater than approximately 100 nm, for example, approximately 10-80 nm;optional electron-injecting layer (d), usually no greater thanapproximately 100 nm, for example, approximately 10-80 nm; and cathodelayer (e), usually no greater than approximately 1000 nm, for example,approximately 30-500 nm. If the anode layer (a) or the cathode layer (e)needs to transmit at least some light, the thickness of such layer maynot exceed approximately 100 nm.

The location of the electron-hole recombination zone in the device, andthus the emission spectrum of the device, can be affected by therelative thickness of each layer. For example, when a potentiallight-emitting compound, such as Alq₃ is used in the electron transportlayer (d), the electron-hole recombination zone can lie within the Alq₃layer.

The emission would then be that of Alq₃, and not a desired sharpemission. Thus, the thickness of the electron-transport layer should bechosen so that the electron-hole recombination zone lies within thelight-emitting layer (i.e., active layer (c)). The desired ratio oflayer thicknesses can depend on the exact nature of the materials used.

The efficiency of the devices made with metal complexes can be furtherimproved by optimizing the other layers in the device. For example, moreefficient cathodes such as Ca, Ba, Mg/Ag, or LiF/Al can be used. Shapedsubstrates and hole transport materials that result in a reduction inoperating voltage or increase quantum efficiency are also applicable.Additional layers can also be added to tailor the energy levels of thevarious layers and facilitate electroluminescence.

Depending upon the application of the electronic device, the activelayer (c) can be a light-emitting layer that is activated by a signal(such as in a light-emitting diode) or a layer of material that respondsto radiant energy and generates a signal with or without an appliedpotential (such as detectors or voltaic cells). Examples of electronicdevices that may respond to radiant energy are selected fromphotoconductive cells, photoresistors, photoswitches, phototransistors,and phototubes, and photovoltaic cells. After reading thisspecification, skilled artisans will be capable of selecting material(s) that for their particular applications.

In OLEDs, electrons and holes, injected from the cathode (e) and anode(a) layers, respectively, into the photoactive layer (c), form negativeand positively charged polarons in the active layer (c). These polaronsmigrate under the influence of the applied electric field, forming apolaron exciton with an oppositely charged species and subsequentlyundergoing radiative recombination. A sufficient potential differencebetween the anode and cathode, usually less than approximately 20 volts,and in some instances no greater than approximately 5 volts, may beapplied to the device. The actual potential difference may depend on theuse of the device in a larger electronic component. In many embodiments,the anode layer (a) is biased to a positive voltage and the cathodelayer (e) is at substantially ground potential or zero volts during theoperation of the electronic device. A battery or other power source (s)may be electrically connected to the electronic device as part of acircuit.

In other embodiments, the metal complex compound can be used as a chargetransport material in layer (b) or (d).

The compound does not need to be in a solid matrix diluent (e.g., hostcharge transport material) when used in layer (b) (c), or (d) in orderto be effective. A layer greater than approximately 1% by weight of themetal complex compound, based on the total weight of the layer, and upto substantially 100% of the complex compound can be used as the activelayer (c). Additional materials can be present in the active layer (c)with the complex compound. For example, a fluorescent dye may be presentto alter the color of emission.

A diluent may also be added. The diluent can be a polymeric material,such as poly(N-vinyl carbazole) and polysilane. It can also be a smallmolecule, such as 4,4′-N,N′-dicarbazole biphenyl or tertiary aromaticamines. When a diluent is used, the complex compound is generallypresent in a small amount, usually less than 20% by weight, preferablyless than 10% by weight, based on the total weight of the layer.

The metallic complexes may be used in applications other than electronicdevices. For example, the complexes may be used as catalysts orindicators (e.g., oxygen-sensitive indicators, phosphorescent indicatorsin bioassays, or the like).

The following examples illustrate certain features and advantages of thepresent invention. They are intended to be illustrative of theinvention, but not limiting. All percentages are by weight, unlessotherwise indicated.

EXAMPLES Example 1

a) 41.6 g (0.20 mol) of 9,10-dioxophenanthrene are suspended undernitrogen in 500 ml of acetic acid and treated at 106° C. with 2.4 g(0.01 mol) of dibenzoyl peroxide, followed by dropwise addition of 35.2g (0.22 mol) of bromine during 75 min. An additional 35.2 g (0.22 mol)of bromine are added dropwise during 75 min, followed by another 25.6 g(0.16 mol) of bromine during 45 min. The reaction mixture is furtherheated for 3 h at 106° C., followed by stirring at room temperature for20 h. The yellow suspension is filtered, washed with a small amount ofacetic acid, followed by washing with 500 ml of water and 500 ml ofethanol. The remaining yellow solid (80 g) is dissolved in hotN,N-dimethylformamide (DMF), and the solution cooled down to roomtemperature, until precipitation started. Precipitation is completed bystirring at room temperature for one hour. The precipitated solid isfiltered off, washed with a small amount of DMF, and additional amountsof methanol and hexane. The title product is obtained as a yellow powderafter drying under vacuum at 50° C. (yield: 34.8 g (61%)).

b) 1.6 g (26.8 mmol) of 1,2-diaminoethane are added under nitrogen to asuspension of 6.4 g (22.3 mmol) of the product of example 1a in 100 mlof toluene. The yellow suspension is heated under reflux for 24 h usinga water separator. The resulting brownish suspension is treated with10.0 g of manganese(IV)oxide at 104° C. Heating is continued underreflux until no intermediate product is visible anymore on the TLC(after 10 min reaction time). The hot black suspension is filtered andthe solid residue rinsed with 100 ml of toluene. The filtrate isconcentrated and further dried under vacuum, giving the title product asyellow solid (yield: 6.3 g (91%)).

c) 3.1 g (0.01 mol) of the product of example 1b, and 1.34 g (0.011 mol)of phenylboronic acid are suspended under argon in 100 ml of dioxane and350 ml of toluene. 0.02 g (0.09 mmol) of palladium(II) acetate and 0.25g (0.61 mmol) of 2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl areadded, and the reaction mixture is degassed with argon. A degassedsolution of 11.5 g (0.05 mol) of potassium phosphate hydrate in 25 ml ofwater is added. The yellow suspension is heated under reflux for 6 h.The resulting grey biphasic solution is filtered through Hyflo and thefilter cake washed with toluene. The filtrate is further extracted withwater (3×50 ml), and the organic phase concentrated and dried undervacuum, giving the title product as a light yellow solid (yield: 3.0 g(quantitative)). Melting point: 176-178° C.

Example 2

a) The title product isomer mixture is prepared according to theprocedure of example 1b, with 1,2-diaminopropane. The ¹H-NMR spectrashows two product isomers formed in a 1:1-ratio.

b) 16.2 g (0.05 mol) of the product isomer mixture of example 2a, and6.7 g (0.055 mol) of phenylboronic acid are suspended under argon in 100ml of dioxane and 300 ml of toluene. 0.11 g (0.49 mmol) of palladium(II)acetate and 1.23 g (3.0 mmol) of2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl are added, and thereaction mixture is degassed with argon. A degassed solution of 57.6 g(0.25 mol) of potassium phosphate hydrate in 100 ml of water is added.The yellow suspension is heated under reflux for 2 h. The resulting greybiphasic solution is filtered through Hyflo and the filter cake washedwith toluene. The filtrate is further extracted with water (3×150 ml),the organic phase concentrated, and the resulting solid recrystallizedfrom 700 ml of acetone. The solid is filtered off and dried under vacuumat 50° C., giving the title product isomer mixture as a light yellowsolid (yield: 8.2 g (51%)). Melting point: 158-162° C.

Example 3

a) 5.4 g (72 mmol) of 1,2-diaminopropane are added to a suspension of22.0 g (0.06 mol) of 3,6-dibromo-9,10-dioxophenanthrene in 600 ml oftoluene. The brown suspension is heated under reflux for 24 h using awater separator. The resulting brownish suspension is treated with 30.0g of manganese(IV)oxide at 93° C., followed by the addition of 600 ml oftoluene. Heating is continued under reflux until no intermediate productis visible anymore on the TLC (after 45 min reaction time). The hotblack suspension is filtered and the solid residue rinsed with 400 ml ofhot toluene. The filtrate is cooled down until precipitation of a whitesolid started. The solid is separated and further dried under vacuumgiving a light beige solid (yield: 22.2 g (92%)).

b) 20.1 g (0.05 mol) of the product of example 3a, and 13.4 g (0.11 mol)of phenylboronic acid are suspended under argon in 100 ml of dioxane and350 ml of toluene. 0.11 g (0.49 mmol) of palladium(II) acetate and 1.23g (3 mmol) of 2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl areadded, and the reaction mixture is degassed with argon. A degassedsolution of 57.6 g (0.25 mol) of potassium phosphate hydrate in 70 ml ofwater is added. The yellow suspension is heated under reflux for 90 min.The resulting grey biphasic solution is filtered through Hyflo and thefilter cake washed with hot toluene, followed by washing with ethanol.The filtrate is suspended with water, followed by filtration, suspensionwith water, filtration, and washing with ethanol. The resulting solid isdried under vacuum at 55° C. giving a light pink solid (yield: 17.8 g(90%)). Melting point: 197-199° C.

Example 4

a) 4.86 g (65.6 mmol) of 1,2-diaminopropane are added to a suspension of20.0 g (54.6 mmol) of 3,6-dibromo-9,10-dioxophenanthrene in 300 ml ofethanol (99%). The reaction mixture is heated under reflux for 6 h. 400ml of acetic acid are added to the reaction mixture and heating underreflux is continued for 19 h. The resulting beige suspension is cooleddown to room temperature, filtered, and washed with ethanol, followed bywashing with saturated aqueous sodium bicarbonate, water, and ethanol.20.2 g of a beige solid are obtained after filtration and drying undervacuum. The solid is further soxhlet extracted with toluene giving thetitle compound as a light beige solid (yield: 13.0 g (59%)).

b) 1.00 g (2.49 mmol) of the product of example 4a, and 1.03 g (6.22mmol) of 4-ethoxyphenyl-boronic acid and 61 mg (0.15 mmol) of2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl are dissolved in 30 mlof toluene and 30 ml of dioxane. The reaction mixture is degassed withargon. 5.6 mg (0.025 mmol) of palladium(II) acetate are added and thereaction mixture is degassed with argon. A degassed solution of 2.86 g(12.4 mmol) of potassium phosphate hydrate in 5 ml of water is added.The reaction mixture is heated under reflux for 3 h. 30 ml of a 1%aqueous NaCN solution is added and the reaction mixture is stirred for 2h at room temperature. The solution is poured into 150 ml of methanoland the product is filtered off. The product is washed with water andmethanol giving the title compound as a light yellow solid (yield: 0.92g (76%)). Melting point: 249.0-251.5° C.

Example 5

4.2 g (0.044 mol) of sodium tert-butylate are added to 12.4 g (0.04 mol)of the product of example 1b in 300 ml of toluene. The reaction mixtureis degassed with argon and 0.45 g (2 mmol) of palladium(II) acetate and4.0 ml (4 mmol) of a 1.0M solution of tri-tert-butylphosphine in tolueneare added, followed by degassing with argon, and addition of 6.8 g (0.04mol) of diphenylamine. The reaction mixture is stirred for 30 min at110° C., cooled down to room temperature and stirred together with 1 gof activated charcoal. The mixture is filtered over silica gel and thesilica gel washed with 200 ml of ethyl acetate. The collected organicphases are extracted with water (2×200 ml) and concentrated undervacuum, providing a yellow-brownish resin. The resin is dissolved with50 ml of hot dichloromethane, and cooled down to room temperature. Aprecipitate is formed which is filtered off, washed with a 20 ml ofacetone, and dried under vacuum, giving the title product as a yellowsolid (yield: 13.0 g (82%)). Melting point: 179-181° C.

Example 6

3.2 g (0.033 mol) of sodium tert-butylate are added to 9.7 g (0.03 mol)of the product of example 2a in 300 ml of toluene. The reaction mixtureis degassed with argon and 0.34 g (1.5 mmol) of palladium(II) acetateand 3.0 ml (3 mmol) of a 1.0M solution of tri-tert-butylphosphine intoluene are added, followed by degassing with argon, and addition of 5.1g (0.03 mol) of diphenylamine. The reaction mixture is stirred for 30min at 110° C., cooled down to room temperature and stirred togetherwith 1 g of activated charcoal. The mixture is filtered over silica geland the silica gel washed with 200 ml of ethyl acetate. The collectedorganic phases are extracted with water (2×200 ml) and concentratedunder vacuum. The product is recrystallized from acetone, the solidfiltered off, and washed with cold acetone, giving the title productisomer mixture as a yellow solid (yield: 9.6 g (78%)). The ¹H-NMRspectra shows two product isomers formed in a 1:1-ratio. Melting point:165-168° C.

Example 7

a) 3.94 g (65.6 mmol) of 1,2-diaminoethane are added under nitrogen to20.0 g (54.6 mmol) of 3,6-dibromo-9,10-dioxophenanthrene in 350 ml ofwater free ethanol. The reaction mixture is refluxed for 8 h. 400 ml ofglacial acetic acid are added and reflux is continued for additional 9 hunder air. The reaction mixture is cooled to 25° C., the product isfiltered off, washed with ethanol and dried under vacuum at 50° C. Thecrude product is further soxhlet extracted with toluene giving the titlecompound as a light beige solid (yield: 16.0 g (76%). Melting point:278.0-282.0° C.

b) 2.27 g (23.6 mmol) of sodium tert-butylate are added to 4.36 g (11.2mmol) of the product of example 7a in 44 ml of toluene. The reactionmixture is degassed with argon and 0.13 g (0.56 mmol) of palladium(II)acetate and 0.23 g (1.12 mmol) of tri-tert-butylphosphine are added,followed by degassing with argon. A degassed solution of 3.80 g (22.5mmol) of diphenylamine in 15 ml toluene is added. The reaction mixtureis stirred for 1 h at 110° C. under argon, cooled down to roomtemperature and extracted with CH₂Cl₂/water. The organic phase isconcentrated and the resulting crude product dissolved in CH₂Cl₂,filtered over silica gel and the silica gel is washed with a smallamount of CH₂Cl₂. The filtrate is concentrated, and the resulting soliddried under vacuum giving the title compound (yield: 5.52 g (87%)).Melting point: 204° C.

c) 12.9 g (0.033 mol) of the product of example 7a, and 8.94 g (0.073mol) of phenylboronic acid are suspended under argon in 75 ml of dioxaneand 250 ml of toluene. 0.075 g (0.33 mmol) of palladium(II) acetate and0.82 g (2 mmol) of 2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl areadded, and the reaction mixture is degassed with argon. A degassedsolution of 46 g (0.2 mol) of potassium phosphate hydrate in 70 ml ofwater is added. The yellow suspension is heated under reflux for 4 h.The resulting grey biphasic solution is filtered through Hyflo and thefilter cake washed with hot toluene, followed by washing with ethanol.The filtrate is suspended with water, followed by filtration, suspensionwith water, filtration, and washing with ethanol. The resulting solid isdried under vacuum at 55° C. giving a light yellow solid (yield: 8.6 g(68%)). Melting point: 254-256° C.

Example 8

6.2 g (0.065 mol) of sodium tert-butylate are added to 12.1 g (0.03 mol)of the product of example 3a in 240 ml of toluene. The reaction mixtureis degassed with argon and 0.34 g (1.5 mmol) of palladium(II) acetateand 3.0 ml (3 mmol) of a 1.0M solution of tri-tert-butylphosphine intoluene are added, followed by degassing with argon. The reactionmixture is heated up to 90° C., treated with 10.7 g (0.063 mol) ofdiphenylamine in 60 ml of toluene, and heating continued for 3 h at 90°C. The reaction mixture is cooled down to room temperature, two timesfiltered over silica gel followed by washing of the silica gel withtoluene. The collected organic phases are concentrated, giving a darkbrown viscous oil, which solidifies upon standing at room temperature.The crude solid is decocted two times in 150 ml of isopropanol, givingthe title product as a dark yellow solid (yield: 12.3 g (80%)).

Example 9

a) 18.6 g (0.31 mol) of 1,2-diaminoethane are added under nitrogen to55.0 g (0.26 mol) of 9,10-dioxophenanthrene in 1000 ml of toluene. Thered suspension is heated under reflux for 24 h using a water separator(amount of water separated: ca. 1 ml). The resulting brownish suspensionis treated with 50.0 g of manganese(IV)oxide at 84° C., and heatingcontinued under reflux until no intermediate product is visible anymoreon the TLC. The hot black suspension is filtered and the solid residuerinsed with 200 ml of toluene. The solution is concentrated and theresulting solid further dried under vacuum, giving the title compound asa light yellowish solid (yield: 58.0 g (97%)).

b) 46.0 g (0.2 mol) of the product of example 9a are suspended underargon in 700 ml of THF and cooled down to 0-5° C. The resulting lightbrownish suspension is dropwise treated at 0-5° C. over one hour with126.0 g (0.2 mol) of a 1.9M phenyl lithium solution in dibutyl ether.Stirring is continued at the same temperature for 10 min, and for anadditional 20 min up to room temperature. 15 ml of water are added firstat room temperature giving a dark yellow suspension, followed by theaddition of 200 ml of ethyl acetate and 70 g of manganese(IV) oxide. Theblack suspension is stirred at room temperature overnight, filtered, andthe solid residue first washed with ethyl acetate, followed by extensivewashing with dichloromethane (3×2000 ml). The combined dichloromethaneeluents are concentrated under vacuum giving the title product as awhite solid (yield: 46.3 g (76%)). Melting point: 204-206° C.

c) 10.0 g (43.4 mmol) of the product of example 9a are suspended underargon in 100 ml of THF and cooled down to −75° C. The resulting lightbrown suspension is dropwise treated over 30 min with 25 ml (48 mmol) ofa 30-35% 2-ethylhexyllithium solution in heptane and stirring continuedat the same temperature for 15 min, and for an additional 70 min up toroom temperature. 100 ml of ethyl acetate and 10 g of manganese(IV)oxide are added and the black suspension stirred at 65° C. during 23 h.The suspension is filtered and the solid residue washed with 50 ml ofethyl acetate, followed by concentration of the filtrate. The residue isfurther eluted over silica gel using toluene as eluent. The combinedfractions are concentrated under vacuum giving a light pink solid. Thesolid is further stirred in hot methanol, cooled down to roomtemperature, filtered, and washed with methanol. The resulting solid isdried under vacuum at 50° C., giving the title product as a white solid(yield: 4.5 g (31%)). Melting point: 58-59° C.

d) The title product is prepared according to the procedure of example9c, with the product of example 9a, and with a 2.5M solution ofn-butyllithium in hexane, giving the title product as a white solid in49% yield after recrystallization from ethanol. Melting point: 66-67° C.

e) The title product is prepared according to the procedure of example9c, with the product of example 9a, and with a 1.5M solution oftert-butyllithium in pentane, giving the title product as a light beigesolid in 16% yield. Melting point: 61-62° C.

f) The title product is prepared according to the procedure of example9a, using 1,2-diaminocyclohexane, and with a 2.5M solution ofn-butyllithium in hexane, giving the title product as a white solid in49% yield. Melting point: 210° C.

Example 10

13.3 g (62.5 mmol) of 4-bromo-4-tert-butyl-benzene in 60 ml of diethylether are slowly treated under argon with 40 ml of a 1.5M tert-butyllithium solution in pentane during 30 min at −75° C., followed by theaddition of 30 ml of THF, giving a light yellow solution (=solution A).11.5 g (0.05 mol) of the product of example 9a are dissolved in 250 mlof THF and slowly treated with solution A at −35° C. during one hour.The cooling bath is removed, and 250 ml of ethyl acetate and 40 g ofmanganese(IV) oxide added as soon as room temperature has been reached.The dark suspension is stirred during 24 h at room temperature,filtered, washed with dichloromethane, and concentrated under vacuum.The residue is suspended in ethanol, then filtered, and further driedunder vacuum, giving the title product as a white solid (yield: 10.1 g(56%)). Melting point: 186-187° C.

Example 11

6.3 g (28 mmol) of 4-bromobenzotrifluoride in 30 ml of diethyl ether areslowly treated under argon with 15 ml of a 1.5M tert-butyl lithiumsolution in pentane during 30 min at −75° C., giving a yellow solution(=solution A). 4.3 g (18.7 mmol) of the product of example 9a aredissolved in 50 ml of THF and slowly treated with solution A at −15° C.during 30 min, followed by the addition of 100 ml of ethyl acetate, andsubsequent warming up to 18° C. Manganese(IV) oxide (20 g) is added andthe dark suspension stirred during 24 h at room temperature. Anadditional 20 g of manganese(IV) oxide are added and stirring continueduntil no more intermediate product is visible by TLC. The darksuspension is filtered, washed with ethyl acetate, concentrated, andstirred with hot hexane until a solid formed. The solid is separated andsuspended in ethyl acetate, followed by filtration over silica gel usingethyl acetate as eluent. The combined eluents are concentrated and driedunder vacuum giving the title product as a white solid (yield: 4.2 g(74%)). Melting point: 222-224° C.

Example 12

10.95 g (62.5 mmol) of 1-bromo-fluorobenzene in 60 ml of THF are slowlytreated under argon with 40 ml of a 1.5M tert-butyl lithium solution inpentane during 30 min at −75° C., followed by the addition of 30 ml ofTHF, giving a light yellow solution (=solution A). 11.5 g (0.05 mol) ofthe product of example 9a are dissolved in 250 ml of THF and slowlytreated with solution A at −35° C. during one hour. The cooling bath isremoved, and 250 ml of ethyl acetate and 40 g of manganese(IV) oxideadded as soon as room temperature has been reached. The dark suspensionis stirred during 24 h at room temperature, filtered through a filteraid (2 cm of Hyflo). The solid is washed with ethyl acetate first,followed by washing with 500 ml of dichloromethane and 500 ml ofacetone. The ethyl acetate fraction is concentrated under vacuum, givingthe title product containing side products (12.3 g isolated solid). Thedichloromethane and acetone fractions are combined and concentratedunder vacuum, giving the title product in high purity as a white solid(yield: 5.0 g (28%)). Melting point: 206-208° C.

Example 13

9.7 g (0.03 mol) of 1-bromo-triphenylamine in 60 ml of THF are slowlytreated under argon with 24 ml of a 1.5M tert-butyl lithium solution inpentane during 45 min at −75° C., giving a brown solution (=solution A).6.9 g (0.03 mol) of the product of example 9a are dissolved in 150 ml ofTHF and slowly treated with solution A at −50° C. during one hour. Thecooling bath is removed, and 1 ml of water and 15 g of manganese(IV)oxide added as soon as room temperature has been reached. The darksuspension is stirred during 2 h at room temperature, filtered throughHyflo, and the filtrate concentrated under vacuum. The resulting solidis recrystallized from isopropanol first, washed with acetone, andrecrystallized from acetone. The solid is filtered off, dried undervacuum, giving the title product as a light yellow solid (yield: 2.5 g(18%)). Melting point: 216-218° C.

Example 14

13.0 g (62.5 mmol) of 1-bromonaphthalene in 60 ml of THF are slowlytreated under argon with 40 ml of a 1.5M tert-butyl lithium solution inpentane during 40 min at −75° C., giving a yellow solution (=solutionA). 11.5 g (50 mmol) of the product of example 9a are dissolved in 250ml of THF and slowly treated with solution A at −30° C. during 30 min,followed by warming up to room temperature. Manganese(IV) oxide (20 g)is added and the dark suspension stirred during 24 h at roomtemperature. An additional 20 g of manganese(IV) oxide are added andstirring continued until no more intermediate product is visible by TLC.The dark suspension is filtered, washed with dichloromethane, andconcentrated under vacuum. The resulting yellow solid is suspended inhot ethyl acetate, filtered, rinsed with ethyl acetate, and dried undervacuum, giving a beige solid (yield: 7.7 g (43%)). Melting point:205-206° C.

Example 15

13.0 g (62.5 mmol) of 2-bromonaphthalene in 60 ml of THF are slowlytreated under argon with 40 ml of a 1.5M tert-butyl lithium solution inpentane at −75° C. during 30 min, giving a yellow solution (=solutionA). 11.5 g (50 mmol) of the product of example 9a are dissolved in 250ml of THF and slowly treated with solution A at −30° C. during 40 min,followed by warming up to room temperature. Manganese(IV) oxide (20 g)is added and the dark suspension stirred during 24 h at roomtemperature. The dark suspension is filtered, washed withdichloromethane, and concentrated under vacuum. The resulting yellowsolid is suspended in hot ethyl acetate, filtered, rinsed with ethylacetate, and dried under vacuum, giving a light beige solid (yield: 8.3g (47%)). Melting point: 216-217° C.

Example 16

a) 44.5 g (0.6 mol) of 1,2-diaminopropane are added under nitrogen to104 g (0.5 mol) of 9,10-dioxophenanthrene in 2000 ml of toluene. The redsuspension is heated under reflux for 24 h using a water separator. Theresulting brownish suspension is treated with 200 g ofmanganese(IV)oxide at 88° C., and heating continued under reflux untilno intermediate product is visible anymore on the TLC. The hot blacksuspension is filtered through silica gel (5 cm layer), and the silicagel layer rinsed with 200 ml of hot toluene. The collected eluents areconcentrated and dried under vacuum, giving the title product as acolorless solid (yield: 103 g (92%)).

b) The title product is prepared according to the procedure of example9b, with 12.2 g (0.05 mol) of the product of example 16a, 31.2 ml of a1.6M phenyl lithium solution in dibutyl ether at 0-5° C., followed by anadditional 8 ml of phenyl lithium solution at 22° C., and 15 g ofmanganese(IV) oxide. The resulting black suspension is filtered, and thesolid residue washed with dichloromethane. The collected eluents areconcentrated and dried under vacuum giving the title product as yellowsolid (yield: 16.0 g (quantitative)). Melting point: 164-166° C.

c) The title product is prepared according to the procedure of example9c, with the product of example 16a, and with a 2.5M solution ofn-butyllithium in hexane, giving the title product as a white solid in57% yield. Melting point: 103° C.

Example 17

The title product isomer mixture is prepared according to the procedureof example 9b, with the product of example 1c as starting material. The¹H-NMR spectra shows two product isomers formed in a 1:1-ratio. Meltingpoint: 215-216° C.

Example 18

3.8 g (0.01 mol) of the product of example 7c are suspended under argonin 50 ml of diethyl ether and cooled down to 0° C. The resulting lightyellow suspension is dropwise treated at 2° C. over 20 min with 5.3 ml(0.01 mol) of a 1.9M phenyl lithium solution in dibutyl ether. Stirringis continued up to room temperature for 35 min. An additional 2 ml ofphenyl lithium solution are added and stirring continued for 15 min. Theresulting dark suspension is treated with 5 g of manganese(IV) oxide andstirred at room temperature for 30 min. The black suspension isfiltered, and the remaining solid washed with 300 ml of ethyl acetate,followed by 300 ml of toluene, and 200 ml of dichloromethane, andfurther decocting in 300 ml of toluene. All toluene and dichloromethanewashings are combined and concentrated under vacuum. The residue isdecocted in 200 ml of toluene first, the resulting yellow suspensionfiltered, and the remaining solid dried under vacuum, giving the productas a yellow solid. Melting point: 275-276° C.

Example 19

5.4 g (24 mmol) of 4-bromobenzotrifluoride in 30 ml of diethyl ether areslowly treated under argon with 14.7 ml of a 1.5M tert-butyl lithiumsolution in pentane during 30 min at −75° C., giving a yellow solution(=solution A). 7.65 g (0.02 mol) of the product of example 7c aredissolved in 250 ml of THF and slowly treated with solution A during 30min at −35° C., and subsequent warming up to room temperature.Manganese(IV) oxide (20 g) is added and the dark suspension stirredduring 24 h at room temperature. The dark suspension is filtered, washedwith ethyl acetate and concentrated. The solid is suspended in ethylacetate, filtered, and dried under vacuum giving the title product as alight yellow solid (yield: 5.0 g (48%)). Melting point: 279-283° C.

Example 20

5.6 g (0.01 mol) of the product of example 7b are suspended under argonin 100 ml of diethyl ether and cooled down to 0° C. The resulting yellowsuspension is dropwise treated over 20 min at 2° C. with 6.3 ml of a1.6M phenyl lithium solution in diethyl ether. Stirring is continued for20 min at 2° C., and then up to room temperature for 15 min. Anadditional 3 ml of phenyl lithium solution are added and stirringcontinued for 25 min. The resulting red suspension is diluted with 100ml of ethyl acetate, treated with 15 g of manganese(IV) oxide andstirred for 24 h at room temperature. The black suspension is filtered,the remaining solid washed with ethyl acetate, and concentrated undervacuum. The dark resin is taken up in 50 ml of ethyl acetate, providinga precipitate by heating the mixture under relux. The suspension isfiltered, the solid decocted in 50 ml of ethyl acetate, filtered, anddried under vacuum at 50° C., giving the title product as a yellow solid(yield: 3.9 g (61%)). Melting point: 256-259° C.

Example 21

6.2 g (0.02 mol) of the product of example 1b, and 3.1 g (0.022 mol) of4-fluorobenzeneboronic acid are suspended under argon in 50 ml ofdioxane and 150 ml of toluene. 0.04 g (0.18 mmol) of palladium(II)acetate and 0.5 g (1.2 mmol) of2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl are added, and thereaction mixture is degassed with argon. A degassed solution of 23.0 g(0.1 mol) of potassium phosphate hydrate in 50 ml of water is added. Theyellow suspension is heated under reflux for 2 h. The resulting greybiphasic solution is filtered through Hyflo and the filter cake washedwith toluene. The filtrate is further extracted with water (3×50 ml),and the organic phase concentrated. The resulting solid isrecrystallized from 250 ml of ethyl acetate, filtered, washed with asmall amount of cold ethyl acetate, and dried under vacuum, giving thetitle product as a light yellow solid (yield: 4.7 g (63%)). Meltingpoint: 200-201° C.

Example 22

6.2 g (0.02 mol) of the product of example 1b, and 4.1 g (0.022 mol) of4-(trifluoromethyl)-benzeneboronic acid are suspended under argon in 50ml of dioxane and 150 ml of toluene. 0.04 g (0.18 mmol) of palladium(II)acetate and 0.5 g (1.2 mmol) of2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl are added, and thereaction mixture is degassed with argon. A degassed solution of 23.0 g(0.1 mol) of potassium phosphate hydrate in 50 ml of water is added. Theyellow suspension is heated under reflux for 2 h. The resulting greybiphasic solution is filtered through Hyflo and the filter cake washedwith toluene. The filtrate is further extracted with water (3×50 ml),and the organic phase concentrated. The resulting solid isrecrystallized from 250 ml of ethyl acetate, filtered, washed with asmall amount of cold ethyl acetate, and dried under vacuum, giving thetitle product as a light yellow solid (yield: 4.7 g (63%)). Meltingpoint: 207-208° C.

Example 23

6.2 g (0.02 mol) of the product of example 1b, and 5.67 g (0.022 mol) of3,5-bis(trifluoromethyl)-benzeneboronic acid are suspended under argonin 50 ml of dioxane and 150 ml of toluene. 0.04 g (0.18 mmol) ofpalladium(II) acetate and 0.5 g (1.2 mmol) of2-dicyclohexyl-phosphino-2′,6′-dimethoxybiphenyl are added, and thereaction mixture is degassed with argon. A degassed solution of 23.0 g(0.1 mol) of potassium phosphate hydrate in 50 ml of water is added. Theyellow suspension is heated under reflux for 2 h. The resulting greybiphasic solution is filtered through Hyflo and the filter cake washedwith toluene. The filtrate is further extracted with water (3×50 ml),and the organic phase concentrated. The resulting solid isrecrystallized from 250 ml of acetone, filtered, washed with a smallamount of cold acetone, and dried under vacuum, giving the title productas a light yellow solid (yield: 6.8 g (77%)). Melting point: 213-214° C.

Example 24

7.2 g (22.5 mmol) of the product isomer mixture of example 2b and 3.9 g(10.7 mmol) of iridium(III)chloride hydrate (52.84% iridium-content) aresuspended at room temperature under nitrogen in 100 ml of2-ethoxyethanol. The grey-black suspension is heated up to 116° C. andkept at this temperature for 19 h. The orange red suspension isfiltered, washed with 2-ethoxyethanol first, followed by ethanol, andfurther dried under vacuum, giving the title product as an orange powder(yield: 8.2 g (88%)).

Example 25

0.96 g (1.99 mmol) of the product of example 4b and 0.32 g (0.90 mmol)of iridium(III)chloride hydrate are suspended under argon in 80 ml of2-ethoxyethanol and 6 ml of water. The reaction mixture is heated underreflux for 22 h. The reaction mixture is cooled down to 20° C., theproduct is filtered off, followed by washing several times with waterand ethanol. The isolated solid is further dried under vacuum giving thetitle compound as a dark red powder (yield: 0.69 g (68%)).

Example 26

6.6 g (16 mmol) of the product isomer mixture of example 6 and 2.77 g(7.6 mmol) of iridium(III)chloride hydrate (52.84% iridium-content) aresuspended at room temperature under nitrogen in 70 ml of2-ethoxyethanol. The grey-black suspension is heated up to 114° C. andkept at this temperature for 17 h. The dark red suspension is cooleddown to room temperature, diluted with 50 ml of ethanol, filtered,washed with ethanol, and further dried under vacuum. The title productis obtained as an orange-red powder (yield: 7.1 g (89%)).

Example 27

1.0 g (1.77 mmol) of the product of example 7b and 0.31 g (0.84 mmol) ofiridium(III)chloride hydrate are suspended under argon in a mixture of20 ml of 2-ethoxyethanol and 7 ml of water. The reaction mixture isheated under reflux for 19 h. The black reaction mixture is filtered,and then suspended/filtered three times with hot ethanol. The resultingsolid is further dried under vacuum giving a brownish black powder(yield: 0.93 g (82%)).

Example 28

5.5 g (13 mmol) of the product isomer mixture of example 17 and 2.25 g(6.2 mmol) of iridium(III)chloride hydrate (52.84% iridium-content) aresuspended at room temperature under nitrogen in 70 ml of2-ethoxyethanol. The yellow suspension is heated up to 116° C. and keptat this temperature for 18 h. The red suspension is filtered, washedwith 2-ethoxyethanol first, followed by ethanol, and further dried undervacuum, giving the title product as an orange red powder (yield: 5.4 g(89%)).

Examples 24-45

The following diiridium complexes are prepared according to theprocedure reported for example 24-28, giving the products of examples29-45. The respective m/z-values of the product structures have beendetected by HPLC-MS measurements.

Exam- Li- ple gand Diiridium complex 29 1c

L^(a) is

or

30 3b

31 5

32 8

33 9b

34 10

35 11

36 12

37 13

38 14

39 15

40 16b

41 19

42 20

43 21

L^(a) is

or

44 22

L^(a) is

or

45 23

L^(a) is

or

Example 46

4.3 g (2.5 mmol) of the product of example 24, and 2.65 g (25 mmol) ofsodium carbonate are suspended under nitrogen in 100 ml ofethoxyethanol. The dark suspension is treated with 2.3 g (12.5 mmol) of2,2,6,6-tetramethyl-3,5-heptanedione and stirred at 115° C. until nomore starting material is visible by TLC. The resulting dark suspensionis filtered, the remaining solid washed with ethanol and suspended inwater. The suspension is filtered, washed with water and a small amountof ethanol. The solid is dried under vacuum giving the title product asa red powder (yield: 4.2 g (83%)).

Example 47

0.60 g (0.25 mmol) of the product of example 25, and 0.18 g (1.66 mmol)of sodium carbonate are suspended under argon in 20 ml of ethoxyethanol.The dark suspension is treated with 65 mg (0.65 mmol) of acetyl acetoneand stirred at 120° C. for 16 h. The resulting dark red suspension iscooled down to 20° C. and the product is filtered off. After repeatedwashing with ethanol and water a dark red powder is obtained (yield:0.55 g (87%)).

Example 48

3.15 g (1.5 mmol) of the product of example 26, and 1.6 g (15 mmol) ofsodium carbonate are suspended under nitrogen in 70 ml of ethoxyethanol.The red suspension is treated with 1.4 g (7.5 mmol) of2,2,6,6-tetramethyl-3,5-heptanedione and stirred during 75 min at 108°C. The resulting dark red suspension is filtered and the filtratetreated with water. The resulting suspension is filtered, followed bywashing with water and ethanol. The remaining solid is suspended inethanol, filtered, washed with ethanol, and dried under vacuum at 50° C.The title product is obtained as a red powder (yield: 3.2 g (89%)).

Example 49

0.9 g (0.37 mmol) of the product of example 27, and 0.26 g (2.44 mmol)of sodium carbonate are suspended under argon in 10 ml of2-ethoxyethanol. The black suspension is treated with 0.2 g (1.9 mmol)of acetyl acetone and stirred at 100° C. for 21 h. The resulting orangesuspension is cooled down to room temperature, diluted with 50 ml ofwater, filtered, and then washed with 50 ml of ethanol. Washing withwater and ethanol is repeated, and the resulting solid dried undervacuum, giving the title compound as a brownish solid (yield: 0.5 g(50%)).

Example 50

2.3 g (4.9 mmol) of the product of example 13 and 0.85 g (2.31 mmol) ofiridium(III)chloride hydrate (52.84% iridium-content) are suspended atroom temperature under nitrogen in 30 ml of DMF. The yellow suspensionis heated up to 160-165° C. oil bath temperature and kept at thistemperature for 4 h. The dark solution is treated at room temperaturewith 1.2 g (11.6 mmol) of sodium carbonate and 0.85 g (9.3 mmol) ofacetylacetone, and heating continued at 140° C. oil bath temperature onehour. The resulting dark suspension is diluted with 200 ml of ethanol,filtered, and the residue washed with 100 ml of ethanol. The solid issuspended in 200 ml of water, filtered, washed with 200 ml of water,followed by washing with 100 ml of ethanol, and 100 ml of hexane. Theremaining solid is dried under vacuum and further purified via a flashchromatography over silica gel using dichloromethane as eluent. Thetitle product is obtained as a red solid (yield: 0.8 g (29%)).

Example 51

5.0 g (2.5 mmol) of the product of example 28, and 3.0 g (27.7 mmol) ofsodium carbonate are suspended under nitrogen in 100 of ethoxyethanol.The red suspension is treated at room temperature with 2.33 g (12.6mmol) of 2,2,6,6-tetramethyl-3,5-heptanedione and stirred during 30 minat 105° C. The resulting dark red suspension is diluted with 100 ml ofethanol, filtered and washed with ethanol. The remaining solid issuspended in water, filtered, and washed with water. The residue isfurther washed with ethanol and dried under vacuum at 50° C. The titleproduct is obtained as a red powder (yield: 4.0 g (70%)).

Example 52

The title product is prepared according to the procedure of example 50,with the product of example 16a, and with2,2,6,6-tetramethyl-3,5-heptanedione instead of acetylacetone, givingthe product as a red solid in 27% yield.

Example 53

2.0 g (1.1 mmol) of the product of example 34, and 1.52 g (11 mmol) ofpotassium carbonate are suspended under nitrogen in 15 g of phenol. Theorange red suspension is treated with 0.84 g (2.3 mmol) of the productof example 10 and stirred at 200° C. bath temperature for 30 min. Thered suspension is cooled down to room temperature and treated with 100ml of methanol, filtered, and further washed with 200 ml of methanol.The remaining solid is suspended in water, filtered, and washed withwater and methanol. The solid is taken up in 200 ml of ethyl acetate andstirred for 15 min, filtered, and washed with ethyl acetate. The laststep is repeated, followed by drying the solid under vacuum. The titleproduct is obtained as a red powder (yield: 2.4 g (85%)).

Examples 46-78

The iridium complexes are prepared according to examples 46-51, startingfrom the products of examples 24-45. Iridium complexes of examples 75-78are prepared according to the same procedures as described above,starting from the corresponding products of examples 9 and 16, preparingthe diiridium complex according to the procedure of example 24 first,followed by preparation of the final iridium complex according to theprocedure of example 46. The respective m/z-values of the productstructures have been detected by HPLC-MS measurements. Allphotoluminescence (PL) spectra were measured with a Perkin ElmerLuminance Spectrometer LS 50 B. Materials were dissolved in toluene, andthe solution purged with nitrogen in a sealed cuvette. Excitation of thesolutions was done at various wavelengths dependent on the absorptioncharacteristics which were measured before PL measurement was carriedout using the same cuvettes and solutions. The spectrometer is equippedwith two different lamps and covers a wavelength range from 250-800 nm.Colour coordinates CIE x,y were determined from PL spectra andcalculated by a software provided with the spectrometer. The PL quantumefficiency is given relative to Ir(MDQ)₂(acac), described in J.-P. Duanet al., Adv. Mat. 2003, 15, 224, with the PL value of Ir(MDQ)₂(acac)given as 100%.

CIE x,y Example Iridium complex Rel. PL Q.E. (λ_(max)) 54

L^(a) is

or

(C-80) 106% 0.61, 0.39 (604 nm) 55

L^(a) is

or

(D-80) n.d. n.d. 46

L^(a) is

or

(C-81) 137% 0.60, 0.40 (599 nm) 56

L^(a) is

or

(D-81) 107% 0.61, 0.38 (606 nm) 57

(A-156) 124% 0.60, 0.40 (599 nm) 58

(B-156) n.d. 0.61, 0.38 (607 nm) 47

(A-17)  91% 0.60, 0.40 (604 nm) 59

L^(a) is

or

(C-10) n.d. n.d. 60

L^(a) is

or

(D-10) n.d. n.d. 61

L^(a) is

or

(C-1)  80% 0.62, 0.38 (610 nm) 48

L^(a) is

or

(D-1)  90% (611 nm) 49

(A-19) n.d. 0.64, 0.36 (614 nm) 62

(A-1)  67% 0.64, 0.36 (614 nm) 65

(A-157)  98% 0.64, 0.35 (614 nm) 66

(B-157) 102% 0.63, 0.37 (608 nm) 67

(A-158) n.d. 0.65, 0.34 (621 nm) 68

(B-158)  65% 0.67, 0.33 (626 nm) 69

(A-159) n.d. n.d. 70

(B-159)  74% 0.65, 0.35 (618 nm) 50

 76% 0.64, 0.35 (612 nm) (A-151) 71

(A-160)  92% 0.62, 0.37 (606 nm) 72

(A-161)  96% 0.63, 0.36 (611 nm) 73

(B-161) n.d. n.d. 74

(B-162) 142% 0.61, 0.39 (602 nm) 51

L^(a) is

or

(D-79)  83% 0.64, 0.35 (616 nm) 52

104% 0.61, 0.39 (607 nm) 75

(A-163) 141% 0.58, 0.41 (600 nm) 76

(A-164) 120% 0.59, 0.41 (601 nm) 77

(A-166) n.d. n.d. 78

(A-175) n.d. n.d. n.d. = not determined.

APPLICATION EXAMPLES

a) Product of example 62 of the present invention:

7.7 mg of the compound of example 62 (A-1) are dissolved in 50 ml oftoluene (spectroscopic quality), and an aliquot of 0.19 ml furtherdiluted in 5 ml of toluene.

The solution is filled in a quarz cuvette, capped with a stoppercontaining a membrane and purged during 10 minutes with nitrogen througha needle syringe. The photoluminescence spectrum (Perkin Elmer LS 50 B)is measured using an excitation wavelength of 460 nm. In the emissionspectrum only a single band is observed. The maximum emission isobserved at a wavelength of 614 nm, displaying a red emission. Theresultant CIE coordinates are (0.64, 0.36).

b) Product of example 51 of the present invention:

The PL spectrum of the compound of example 51 is measured with the sameprocedure, giving a single band emission, with a maximum emission of 616nm, and CIE coordinates of (0.64, 0.35).

c) product of example 50 of the present invention:

The PL spectrum of the compound of example 50 is measured with the sameprocedure, giving a single band emission, with a maximum emission of 612nm, and CIE coordinates of (0.64, 0.35).

d) Product of example 61 of the present invention:

The PL spectrum of the compound of example 61 is measured with the sameprocedure, giving a single band emission, with a maximum emission of 610nm, and CIE coordinates of (0.62, 0.38).

e) Product of example 58 of the present invention:

The PL spectrum of the compound of example 58 is measured with the sameprocedure, giving a single band emission, with a maximum emission of 607nm, and CIE coordinates of (0.61, 0.38).

f) Product of example 56 of the present invention:

The PL spectrum of the compound of example 56 is measured with the sameprocedure, giving a single band emission, with a maximum emission of 606nm, and CIE coordinates of (0.61, 0.38).

COMPARATIVE APPLICATION EXAMPLE

In a similar manner the compound described in J.-P. Duan et al., Adv.Mat. 2003, 15, 224 as Ir(MDQ)₂ (acac) available from American Dye SourceInc (=ADS076RE). is prepared and measured. The photoluminescencespectrum exhibits a strong emission at 601 nm, displaying an orange-redemission. In the emission spectrum only a single band is observed. Theresultant CIE coordinates are at (0.59, 0.41).

The invention claimed is:
 1. A compound of the formula

wherein R¹, R² and R^(1′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₁-C₁₈ perfluoroalkyl, C₅-C₁₂cycloalkyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C₁₈alkoxy,C₁-C₁₈alkoxy which is substituted by E and/or interrupted by D,C₇-C₂₅arylalkyl, CN,

 or —CO—R²⁸, or R¹ and R² together form a ring, R³, R⁸, R^(3′) andR^(8′) are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl whichis substituted by E and/or interrupted by D, C₁-C₁₈ perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

 —NR²⁵R²⁶, —SR²⁹, or Si(R³⁰)₃, R⁴, R⁷, R^(4′) and R^(7′) areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

 —NR²⁵R²⁶, —SR²⁹, or Si(R³⁰)₃, R⁵, R⁶, R^(5′) and R^(6′) areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which issubstituted by E and/or interrupted by D, C₁-C₁₈perfluoroalkyl,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl,C₂-C₁₈alkynyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, C₇-C₂₅arylalkyl, CN, or —CO—R²⁸,

 —NR²⁵R²⁶, —SR²⁹, Si(R³⁰)₃, R²⁵ and R²⁶ are independently of each otherC₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, or R²⁵ and R²⁶ together withthe nitrogen atom to which they are bonded form a heteroaromatic ring,or ring system, which may optionally be substituted, BU is a bridgingunit, D is —CO—; —COO—; —S—; —SO—; —SO₂—; —O—; —NR^(25′)—; —SiR³⁰R³¹—;—POR³²—; —CR²³═CR²⁴—; or —C≡C—; E is —OR²⁹; —SR²⁹; —NR^(25′)R^(26′);—COR²⁸; —COOR²⁷; —CONR^(25′)R^(26′); —CN; or halogen; G is E,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is interrupted by D, C₁-C₁₈perfluoroalkyl, C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by D, or C₂-C₁₈alkenyl, R²³, R²⁴, R^(25′) and R^(26′)are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which issubstituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkylwhich is interrupted by —O—; R²⁷ and R²⁸ are independently of each otherH; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—,R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl,or C₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by—O—, R³⁰ and R³¹ are independently of each other C₁-C₁₈alkyl,C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C₁-C₁₈alkyl, and R³²is C₁-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted byC₁-C₁₈alkyl, M is Pd, Rh, Re, Pt, or Ir, L is a mono-, or bi-dentateligand, if L is a monodentate ligand, m is 0, or 2, and n is 1, or 2, ifM is Pd, or Pt, m is 0, 2, or 4, and n is 1, 2, or 3, if M is Rh, Ir orRe, if L is a bidentate ligand, m is 0, or 1, and n is 1, or 2, if M isPd, or Pt, m is 0, 1, or 2, and n is 1, 2, or 3, if M is Rh, Ir or Re,with the proviso that at least one of R¹, R², R³, R⁸, R⁴, R⁷, R⁵ and R⁶is different from H and the further proviso that

 are excluded; and with the further proviso that organometalliccomplexes having a structure represented by the general formula

 are excluded, wherein Ar represents an aryl group having 6 to 25 carbonatoms; A¹ represents any one of hydrogen, an alkyl group having 1 to 4carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; A² to A⁸each represent any one of hydrogen, an alkyl group having 1 to 4 carbonatoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen group;M₁₀ represents a metal of Group 9 elements and Group 10 elements; L₁₀represents a monoanionic ligand; and u is 2 when the metal is a Group 9element, and u is 1 when the metal is a Group 10 element.
 2. Thecompound of the formula I, or II according to claim 1, wherein R¹,R^(1′) and R² are independently of each other H, C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, which can optionally be substituted by one to threeC₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,

or CN, or R¹ and R² together form a group

R^(206′), R^(208′), R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹ and R²¹⁰ areindependently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, or C₆-C₂₄aryl,C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl or C₁-C₁₈alkoxy; R³⁰¹,R³⁰², R³⁰³, R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁷ and R³⁰⁸ are independently of eachother H, or C₁-C₁₈alkyl, R³, R⁸, R^(3′) and R^(8′) are independently ofeach other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, or —NR²⁵R²⁶; R⁴, R⁷, R⁴and R⁷ are independently of each other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl whichis substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, C₂-C₁₈alkenyl, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, —NR²⁵R²⁶; R⁵, R⁶, R^(5′)and R^(6′) are H, R²⁵ and R²⁶ are independently of each otherC₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkyl which is interrupted by —O—;or R²⁵ and R²⁶ together with the nitrogen atom to which they are bondedform a heteroaromatic ring system

 m′ is 0, 1, or 2; m″ can be the same or different at each occurence andis 0, 1, 2, or 3; R⁴¹ can be the same or different at each occurence andis Cl, F, CN, N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, aC₁-C₂₅alkoxy group, in which one or more carbon atoms which are not inneighbourhood to each other could be replaced by —NR⁴⁵—, —O—, —S—, or—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced byF, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or morecarbon atoms can be replaced by O, S, or N, and/or which can besubstituted by one or more non-aromatic groups R⁴¹, or two or moregroups R⁴¹ form a ring system; R⁴⁵ is H, a C₁-C₂₅alkyl group, aC₄-C₁₈cycloalkyl group, in which one or more carbon atoms which are notin neighbourhood to each other could be replaced by —NR^(45″)—, —O—,—S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogenatoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxygroup, wherein one or more carbon atoms can be replaced by O, S, or N,and/or which can be substituted by one or more non-aromatic groups R⁴¹,and R^(45″) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group, E is—OR²⁹; —SR²⁹; —NR^(25′)R^(26′), CN, or F; G is E, CF₃, C₁-C₁₈alkyl, orC₂-C₁₈alkenyl, M is Pd, Rh, Re, Pt, or Ir, L is a bidentate ligand, m is0, or 1, and n is 1, or 2, if M is Pd, or Pt, m is 0, 1, or 2, and n is1, 2, or 3, if M is Rh, Ir or Re, and R²⁹; R²⁹; R^(25′) and R^(26′) areas defined in claim 1, with the proviso that at least one of R³, R⁸, R⁴and R⁷ is different from H.
 3. The compound of the formula I accordingto claim 1, wherein at least one of the substituents R¹, R⁴ and R⁷ is agroup —NR²⁵R²⁶, or C₆-C₂₄aryl, which is substituted by —NR²⁵R²⁶, whereinR²⁵ and R²⁶ are independently of each other

wherein R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, whichmay optionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and R²⁶together with the nitrogen atom to which they are bonded form a group offormula

R⁴¹ is H, or C₁-C₂₅alkyl.
 4. The compound of claim 1 having a structure(Va), (Vb), (Vc), (VIa), (VIb), or (VIc) below:

wherein R¹, R^(1′) and R² are independently of each other H,C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, which can optionally be substituted byone to three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄aryl which issubstituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G, or CN, R³, R⁸, R^(3′) and R^(8′) are independently ofeach other H, C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/orinterrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G,C₂-C₁₈alkenyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxy which is substituted by Eand/or interrupted by —O—, C₇-C₂₅arylalkyl, CN, or —NR²⁵R²⁶; R⁴, R⁷,R^(4′) and R^(7′) are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₁-C₁₈alkoxywhich is substituted by E and/or interrupted by —O—, C₇-C₂₅arylalkyl,CN, —NR²⁵R²⁶; R²⁵ and R²⁶ are independently of each other C₆-C₁₈aryl;C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy;C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—; or R²⁵ and R²⁶together with the nitrogen atom to which they are bonded form aheteroaromatic ring system

 m′ is 0, 1, or 2; m″ can be the same or different at each occurence andis 0, 1, 2, or 3; R⁴¹ can be the same or different at each occurence andis Cl, F, CN, N(R⁴⁵)₂, a C₁-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, aC₁-C₂₅alkoxy group, in which one or more carbon atoms which are not inneighbourhood to each other could be replaced by —NR⁴⁵—, —O—, —S—, or—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced byF, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or morecarbon atoms can be replaced by O, S, or N, and/or which can besubstituted by one or more non-aromatic groups R⁴¹, or two or moregroups R⁴¹ form a ring system; R⁴⁵ is H, a C₁-C₂₅alkyl group, aC₄-C₁₈cycloalkyl group, in which one or more carbon atoms which are notin neighbourhood to each other can be replaced by —NR^(45″)—, —O—, —S—,—C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atomscan be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group,wherein one or more carbon atoms can be replaced by O, S, or N, and/orwhich can be substituted by one or more non-aromatic groups R⁴¹, andR^(45″) is H, a C₁-C₂₅alkyl group, or a C₄-C₁₈cycloalkyl group, E is—OR²⁹; —SR²⁹; —NR^(25′)R^(26′), CN or F; G is E, C₁-C₁₈alkyl, CF₃, orC₂-C₁₈alkenyl, R²⁹; R²⁹; R^(25′) and R^(26′) are as defined in claim 1,M² is Rh, Re or Ir, L is a bidentate ligand, and L′″ is a monodentateligand, or a compound of claim 1 having a structure (VIIa), (VIIb),(VIIIa), or (VIIIb) below:

wherein M⁴ is Pd, or Pt, and L, R¹, R², R^(1′), R³, R⁴, R^(3′), R^(4′),R⁷, R⁸, R^(7′) and R^(8′) are as defined above.
 5. The compound offormula I according to claim 1, wherein R² is H, or CH₃, R¹ and R^(1′)are H, C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups, C₆-C₂₄aryl, C₆-C₂₄arylwhich is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which issubstituted by G,

 or CN, R³, R⁸, R^(3′) and R^(8′) are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl; or C₁-C₁₈alkoxy which are interrupted by —O—;C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is interrupted by —O—; or —NR²⁵R²⁶;R⁴, R⁷, R⁴ and R⁷ are independently of each other H, C₁-C₁₈alkyl,C₁-C₁₈alkyl which is substituted by E and/or interrupted by D,C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkoxy which are interrupted by —O—;C₁-C₁₈alkoxy, or C₁-C₁₈alkoxy which is interrupted by —O—; or —NR²⁵R²⁶;R²⁵ and R²⁶ are independently of each other; C₆-C₁₈aryl; C₆-C₁₈arylwhich is substituted by C₁-C₁₈alkyl, or C₁-C₁₈alkoxy; C₁-C₁₈alkyl, orC₁-C₁₈alkoxy which are interrupted by —O—; or R²⁵ and R²⁶ together withthe nitrogen atom to which they are bonded form a heteroaromatic ringsystem

 wherein R⁴¹ is H, or C₁-C₂₅alkyl; M² is Ir, and M⁴ is Pd or Pt, and Lis a bidentate ligand.
 6. The compound of claim 1, wherein the bidentateligand L is a compound of formula

wherein the ring A,

represents an optionally substituted aryl group which can optionallycontain heteroatoms, the ring B,

represents an optionally substituted nitrogen containing aryl group,which can optionally contain further heteroatoms, or the ring A may betaken with the ring B binding to the ring A to form a ring group offormula

wherein R²¹¹, R²¹², R²¹³, and R²¹⁴ are independently of each otherhydrogen, C₁-C₂₄alkyl, C₂-C₂₄alkenyl, C₂-C₂₄alkynyl, aryl, heteroaryl,C₁-C₂₄alkoxy, C₁-C₂₄alkylthio, cyano, acyl, alkyloxycarbonyl, a nitrogroup, or a halogen atom; the ring A represents an optionallysubstituted aryl or heteroaryl group; or the ring A may be taken withthe pyridyl group binding to the ring A to form a ring; the alkyl group,alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxygroup, alkylthio group, acyl group, and alkyloxycarbonyl grouprepresented by R²¹¹, R²¹², R²¹³, and R²¹⁴ may be substituted; or R²¹³and R²¹⁴ or R²¹² and R²¹³ are a group of formula

wherein A⁴¹, A⁴², A⁴³, A⁴⁴, A⁴⁵, and A⁴⁶ are independently of each otherH, halogen, CN, C₁-C₂₄alkyl, C₁-C₂₄ perfluoroalkyl, C₁-C₂₄alkoxy,C₁-C₂₄alkylthio, C₆-C₁₈aryl, which may optionally be substituted by G′,—NR^(25′)R^(26′), —CONR^(25′26′), or —COOR^(27′), or C₂-C₁₀heteroaryl;wherein R^(25′) and R^(26′) are independently of each other C₆-C₁₈aryl,C₇-C₁₈aralkyl, or C₁-C₂₄alkyl, R^(27′) is C₁-C₂₄alkyl, C₆-C₁₈aryl, orC₇-C₁₈aralkyl; G′ is C₁-C₁₈alkyl, —OR³⁰⁵, —SR³⁰⁵, —NR³⁰⁵R³⁰⁶,—CONR³⁰⁵R³⁰⁶, or —CN, wherein R³⁰⁵ and R³⁰⁶ are independently of eachother C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C₁-C₁₈alkyl, orC₁-C₁₈alkoxy; C₁-C₁₈alkyl, or C₁-C₁₈alkyl which is interrupted by —O—;R³⁰⁵ is C₁-C₁₈alkyl, or C₆-C₁₈aryl, and R³⁰⁶ is C₁-C₁₈alkyl, orC₆-C₁₈aryl; or L is a bidentate ligand L′ selected from

 wherein R¹¹ and R¹⁵ are independently of each other hydrogen,C₁-C₈alkyl, C₆-C₁₈aryl, C₂-C₁₀heteroaryl, or C₁-C₈perfluoroalkyl, R¹²and R¹⁶ are independently of each other hydrogen, C₆-C₁₈aryl, orC₁-C₈alkyl, and R¹³ and R¹⁷ are independently of each other hydrogen,C₁-C₈alkyl, C₆-C₁₈aryl, C₂-C₁₀heteroaryl, C₁-C₈ perfluoroalkyl, orC₁-C₈alkoxy, and R¹⁴ is C₁-C₈alkyl, C₆-C₁₀aryl, or C₇-C₁₁aralkyl, R¹⁸ isC₆-C₁₀aryl, R¹⁹ is C₁-C₈alkyl, or C₁-C₈ perfluoroalkyl, R²⁰ is hydrogen,C₁-C₈alkyl, or C₆-C₁₀aryl, R²¹ is hydrogen, C₁-C₈alkyl, or C₁-C₈alkoxy,which may be partially or fully fluorinated, R²² and R²³ areindependently of each other C_(q)(H+F)_(2q+1), or C₆(H+F)₅, R²⁴ can bethe same or different at each occurrence and is selected from H, orC_(q)(H+F)_(2q+1), R⁴⁶ is C₁-C₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, whichis substituted by C₁-C₈alkyl, q is an integer of 1 to 24, p is 2, or 3,or L is a bidentate ligand L″ selected from


7. The compound of claims 6:

Cpd. L R¹ R² R³ and R⁸ R⁴ and R⁷ A-1 A¹⁾ —CH₃ H H

A-2 A¹⁾ —CH₃ H

H A-3 A¹⁾ —CH₃ H H

A-4 A¹⁾ —CH₃ H

H A-5 A¹⁾ —CH₃ H H

A-6 A¹⁾ —CH₃ H

H A-7 A¹⁾ —CH₃ H H

A-8 A¹⁾ —CH₃ H

H A-9 A¹⁾ —CH₃ H H

A-10 A¹⁾ —CH₃ H

H A-11 A¹⁾ —CH₃ H H

A-12 A¹⁾ —CH₃ H

H A-13 A¹⁾ —CH₃ H H

A-14 A¹⁾ —CH₃ H

H A-15 A¹⁾ —CH₃ H H

A-16 A¹⁾ —CH₃ H

H A-17 A¹⁾ —CH₃ H H

A-18 A¹⁾ —CH₃ H

H A-19 A¹⁾ H H H

A-20 A¹⁾ H H

H A-21 A¹⁾ H H H

A-22 A¹⁾ H H

H A-23 A¹⁾ H H H

A-24 A¹⁾ H H

H A-25 A¹⁾ H H H

A-26 A¹⁾ H H

H A-27 A¹⁾ H H H

A-28 A¹⁾ H H

H A-29 A¹⁾ H H H

A-30 A¹⁾ H H

H A-31 A¹⁾ H H H

A-32 A¹⁾ H H

H A-33 A¹⁾ H H H

A-34 A¹⁾ H H

H A-35 A¹⁾ H H H

A-36 A¹⁾ H H

H A-37 A¹⁾ Ph H H

A-38 A¹⁾ Ph H

H A-39 A¹⁾ Ph H H

A-40 A¹⁾ Ph H

H A-41 A¹⁾ Ph H H

A-42 A¹⁾ Ph H

H A-43 A¹⁾ Ph H H

A-44 A¹⁾ Ph H

H A-45 A¹⁾ Ph H H

A-46 A¹⁾ Ph H

H A-47 A¹⁾ Ph H H

A-48 A¹⁾ Ph H

H A-49 A¹⁾ Ph H H

A-50 A¹⁾ Ph H

H A-51 A¹⁾ Ph H H

A-52 A¹⁾ Ph H

H A-53 A¹⁾ Ph H H

A-54 A¹⁾ Ph H

H A-55 A¹⁾

H H

A-56 A¹⁾

H

H A-57 A¹⁾

H H

A-58 A¹⁾

H

H A-59 A¹⁾

H H

A-60 A¹⁾

H

H A-61 A¹⁾

H H

A-62 A¹⁾

H

H A-63 A¹⁾

H H

A-64 A¹⁾

H

H A-65 A¹⁾

H H

A-66 A¹⁾

H

H A-67 A¹⁾

H H

A-68 A¹⁾

H

H A-69 A¹⁾

H H

A-70 A¹⁾

H

H A-71 A¹⁾

H H

A-72 A¹⁾

H

H A-73 A¹⁾

H H

A-74 A¹⁾

H

H A-75 A¹⁾

H H

A-76 A¹⁾

H

H A-77 A¹⁾

H H

A-78 A¹⁾

H

H A-79 A¹⁾

H H

A-80 A¹⁾

H

H A-81 A¹⁾

H H

A-82 A¹⁾

H

H A-83 A¹⁾

H H

A-84 A¹⁾

H

H A-85 A¹⁾

H H

A-86 A¹⁾

H

H A-87 A¹⁾

H H

A-88 A¹⁾

H

H A-89 A¹⁾

H H

A-90 A¹⁾

H

H A-91 A¹⁾

H H

A-92 A¹⁾

H

H A-93 A¹⁾

H H

A-94 A¹⁾

H

H A-95 A¹⁾

H H

A-96 A¹⁾

H

H A-97 A¹⁾

H H

A-98 A¹⁾

H

H A-99 A¹⁾

H H

A-100 A¹⁾

H

H A-101 A¹⁾

H H

A-102 A¹⁾

H

H A-103 A¹⁾

H H

A-104 A¹⁾

H

H A-105 A¹⁾

H H

A-106 A¹⁾

H

H A-107 A¹⁾

H H

A-108 A¹⁾

H

H A-109 A¹⁾

H H

A-110 A¹⁾

H

H A-111 A¹⁾

H H

A-112 A¹⁾

H

H A-113 A¹⁾

H H

A-114 A¹⁾

H

H A-115 A¹⁾

H H

A-116 A¹⁾

H

H A-117 A¹⁾

H H

A-118 A¹⁾

H

H A-119 A¹⁾

H H

A-120 A¹⁾

H

H A-121 A¹⁾

H H

A-122 A¹⁾

H

H A-123 A¹⁾

H H

A-124 A¹⁾

H

H A-125 A¹⁾

H H

A-126 A¹⁾

H

H A-127 A¹⁾

H H

A-128 A¹⁾

H

H A-129 A¹⁾

H H

A-130 A¹⁾

H

H A-131 A¹⁾

H H

A-132 A¹⁾

H

H A-133 A¹⁾

H H

A-134 A¹⁾

H

H A-135 A¹⁾

H H

A-136 A¹⁾

H

H A-137 A¹⁾

H H

A-138 A¹⁾

H

H A-139 A¹⁾

H H

A-140 A¹⁾

H

H A-141 A¹⁾

H H

A-142 A¹⁾

H

H A-143 A¹⁾

H H

A-144 A¹⁾

H

H A-145 A¹⁾

H H

A-146 A¹⁾

H

H A-147 A¹⁾

H H

A-148 A¹⁾

H

H A-149 A¹⁾

H H

A-150 A¹⁾

H

H A-151 A¹⁾

H H H A-152 A¹⁾

H H H A-153 A¹⁾

H H H A-154 A¹⁾

H H H A-155 A¹⁾

H H H A-156 A¹⁾ CH₃ H

A-157 A¹⁾

H H H A-158 A¹⁾

H H H A-159 A¹⁾

H H H A-160 A¹⁾

H H H A-161 A¹⁾

H H H A-162 A¹⁾

CH₃ H H A-163 A¹⁾ 2-ethylhexyl H H H A-164 A¹⁾ n-butyl H H H A-165 A¹⁾tert-butyl H H H A-166 A¹⁾ —(CH₂)₄— H H A-167 A¹⁾ 2-ethylhexyl CH₃ H HA-168 A¹⁾ n-butyl CH₃ H H A-169 A¹⁾ tert-butyl CH₃ H H A-170 A¹⁾2-ethylhexyl H H propyl A-171 A¹⁾ n-butyl H H propyl A-172 A¹⁾tert-butyl H H propyl A-173 A¹⁾ —(CH₂)₄— —(CH₂)₄— H propyl A-174 A¹⁾2-ethylhexyl CH₃ H propyl A-175 A¹⁾ n-butyl CH₃ H propyl A-176 A¹⁾tert-butyl CH₃ H propyl B-1 B¹⁾ —CH₃ H H

B-2 B¹⁾ —CH₃ H

H B-3 B¹⁾ —CH₃ H H

B-4 B¹⁾ —CH₃ H

H B-5 B¹⁾ —CH₃ H H

B-6 B¹⁾ —CH₃ H

H B-7 B¹⁾ —CH₃ H H

B-8 B¹⁾ —CH₃ H

H B-9 B¹⁾ —CH₃ H H

B-10 B¹⁾ —CH₃ H

H B-11 B¹⁾ —CH₃ H H

B-12 B¹⁾ —CH₃ H

H B-13 B¹⁾ —CH₃ H H

B-14 B¹⁾ —CH₃ H

H B-15 B¹⁾ —CH₃ H H

B-16 B¹⁾ —CH₃ H

H B-17 B¹⁾ —CH₃ H H

B-18 B¹⁾ —CH₃ H

H B-19 B¹⁾ H H H

B-20 B¹⁾ H H

H B-21 B¹⁾ H H H

B-22 B¹⁾ H H

H B-23 B¹⁾ H H H

B-24 B¹⁾ H H

H B-25 B¹⁾ H H H

B-26 B¹⁾ H H

H B-27 B¹⁾ H H H

B-28 B¹⁾ H H

H B-29 B¹⁾ H H H

B-30 B¹⁾ H H

H B-31 B¹⁾ H H H

B-32 B¹⁾ H H

H B-33 B¹⁾ H H H

B-34 B¹⁾ H H

H B-35 B¹⁾ H H H

B-36 B¹⁾ H H

H B-37 B¹⁾ Ph H H

B-38 B¹⁾ Ph H

H B-39 B¹⁾ Ph H H

B-40 B¹⁾ Ph H

H B-41 B¹⁾ Ph H H

B-42 B¹⁾ Ph H

H B-43 B¹⁾ Ph H H

B-44 B¹⁾ Ph H

H B-45 B¹⁾ Ph H H

B-46 B¹⁾ Ph H

H B-47 B¹⁾ Ph H H

B-48 B¹⁾ Ph H

H B-49 B¹⁾ Ph H H

B-50 B¹⁾ Ph H

H B-51 B¹⁾ Ph H H

B-52 B¹⁾ Ph H

H B-53 B¹⁾ Ph H H

B-54 B¹⁾ Ph H

H B-55 B¹⁾

H H

B-56 B¹⁾

H

H B-57 B¹⁾

H H

B-58 B¹⁾

H

H B-59 B¹⁾

H H

B-60 B¹⁾

H

H B-61 B¹⁾

H H

B-62 B¹⁾

H

H B-63 B¹⁾

H H

B-64 B¹⁾

H

H B-65 B¹⁾

H H

B-66 B¹⁾

H

H B-67 B¹⁾

H H

B-68 B¹⁾

H

H B-69 B¹⁾

H H

B-70 B¹⁾

H

H B-71 B¹⁾

H H

B-72 B¹⁾

H

H B-73 B¹⁾

H H

B-74 B¹⁾

H

H B-75 B¹⁾

H H

B-76 B¹⁾

H

H B-77 B¹⁾

H H

B-78 B¹⁾

H

H B-79 B¹⁾

H H

B-80 B¹⁾

H

H B-81 B¹⁾

H H

B-82 B¹⁾

H

H B-83 B¹⁾

H H

B-84 B¹⁾

H

H B-85 B¹⁾

H H

B-86 B¹⁾

H

H B-87 B¹⁾

H H

B-88 B¹⁾

H

H B-89 B¹⁾

H H

B-90 B¹⁾

H

H B-91 B¹⁾

H H

B-92 B¹⁾

H

H B-93 B¹⁾

H H

B-94 B¹⁾

H

H B-95 B¹⁾

H H

B-96 B¹⁾

H

H B-97 B¹⁾

H H

B-98 B¹⁾

H

H B-99 B¹⁾

H H

B-100 B¹⁾

H

H B-101 B¹⁾

H H

B-102 B¹⁾

H

H B-103 B¹⁾

H H

B-104 B¹⁾

H

H B-105 B¹⁾

H H

B-106 B¹⁾

H

H B-107 B¹⁾

H H

B-108 B¹⁾

H

H B-109 B¹⁾

H H

B-110 B¹⁾

H

H B-111 B¹⁾

H H

B-112 B¹⁾

H

H B-113 B¹⁾

H H

B-114 B¹⁾

H

H B-115 B¹⁾

H H

B-116 B¹⁾

H

H B-117 B¹⁾

H H

B-118 B¹⁾

H

H B-119 B¹⁾

H H

B-120 B¹⁾

H

H B-121 B¹⁾

H H

B-122 B¹⁾

H

H B-123 B¹⁾

H H

B-124 B¹⁾

H

H B-125 B¹⁾

H H

B-126 B¹⁾

H

H B-127 B¹⁾

H H

B-128 B¹⁾

H

H B-129 B¹⁾

H H

B-130 B¹⁾

H

H B-131 B¹⁾

H H

B-132 B¹⁾

H

H B-133 B¹⁾

H H

B-134 B¹⁾

H

H B-135 B¹⁾

H H

B-136 B¹⁾

H

H B-137 B¹⁾

H H

B-138 B¹⁾

H

H B-139 B¹⁾

H H

B-140 B¹⁾

H

H B-141 B¹⁾

H H

B-142 B¹⁾

H

H B-143 B¹⁾

H H

B-144 B¹⁾

H

H B-145 B¹⁾

H H

B-146 B¹⁾

H

H B-147 B¹⁾

H H

B-148 B¹⁾

H

H B-149 B¹⁾

H H

B-150 B¹⁾

H

H B-151 B¹⁾

H H H B-152 B¹⁾

H H H B-153 B¹⁾

H H H B-154 B¹⁾

H H H B-155 B¹⁾

H H H B-156 B¹⁾ CH₃ H

B-157 B¹⁾

H H H B-158 B¹⁾

H H H B-159 B¹⁾

H H H B-160 B¹⁾

H H H B-161 B¹⁾

H H H B-162 B¹⁾

CH₃ H H B-163 B¹⁾ 2-ethylhexyl H H H B-164 B¹⁾ n-butyl H H H B-165 B¹⁾tert-butyl H H H B-166 B¹⁾ —(CH₂)₄— H H H B-167 B¹⁾ 2-ethylhexyl CH₃ H HB-168 B¹⁾ n-butyl CH₃ H H B-169 B¹⁾ tert-butyl CH₃ H H B-170 B¹⁾2-ethylhexyl H H propyl B-171 B¹⁾ n-butyl H H propyl B-172 B¹⁾tert-butyl H H propyl B-171 B¹⁾ —(CH₂)₄— H H propyl B-174 B¹⁾2-ethylhexyl CH₃ H propyl B-175 B¹⁾ n-butyl CH₃ H propyl B-176 B¹⁾tert-butyl CH₃ H propyl ¹⁾A =

B =

L^(a) is

or

Cpd. L R¹ R² R⁷ = R⁴²⁾ C-1 A¹⁾ —CH₃ H

C-2 A¹⁾ —CH₃ H

C-3 A¹⁾ —CH₃ H

C-4 A¹⁾ —CH₃ H

C-5 A¹⁾ —CH₃ H

C-6 A¹⁾ —CH₃ H

C-7 A¹⁾ —CH₃ H

C-8 A¹⁾ —CH₃ H

C-9 A¹⁾ —CH₃ H

C-10 A¹⁾ H H

C-12 A¹⁾ H H

C-13 A¹⁾ H H

C-14 A¹⁾ H H

C-15 A¹⁾ H H

C-16 A¹⁾ H H

C-17 A¹⁾ H H

C-18 A¹⁾ H H

C-19 A¹⁾ H H

C-20 A¹⁾ Ph H

C-21 A¹⁾ Ph H

C-22 A¹⁾ Ph H

C-23 A¹⁾ Ph H

C-24 A¹⁾ Ph H

C-25 A¹⁾ Ph H

C-26 A¹⁾ Ph H

C-27 A¹⁾ Ph H

C-28 A¹⁾ Ph H

C-29 A¹⁾

H

C-30 A¹⁾

H

C-31 A¹⁾

H

C-32 A¹⁾

H

C-33 A¹⁾

H

C-34 A¹⁾

H

C-35 A¹⁾

H

C-36 A¹⁾

H

C-37 A¹⁾

H

C-38 A¹⁾

H

C-39 A¹⁾

H

C-40 A¹⁾

H

C-41 A¹⁾

H

C-42 A¹⁾

H

C-43 A¹⁾

H

C-44 A¹⁾

H

C-45 A¹⁾

H

C-46 A¹⁾

H

C-47 A¹⁾

H

C-48 A¹⁾

H

C-49 A¹⁾

H

C-50 A¹⁾

H

C-51 A¹⁾

H

C-52 A¹⁾

H

C-53 A¹⁾

H

C-54 A¹⁾

H

C-55 A¹⁾

H

C-56 A¹⁾

H

C-57 A¹⁾

H

C-58 A¹⁾

H

C-59 A¹⁾

H

C-60 A¹⁾

H

C-61 A¹⁾

H

C-62 A¹⁾

H

C-63 A¹⁾

H

C-64 A¹⁾

H

C-65 A¹⁾

H

C-66 A¹⁾

H

C-67 A¹⁾

H

C-68 A¹⁾

H

C-69 A¹⁾

H

C-70 A¹⁾

H

C-71 A¹⁾

H

C-72 A¹⁾

H

C-73 A¹⁾

H

C-74 A¹⁾

H

C-76 A¹⁾

H

C-78 A¹⁾

H

C-79 A¹⁾

H

C-80 A¹⁾ H H

C-81 A¹⁾ CH₃ H

C-82 A¹⁾ 2-ethylhexyl H H C-83 A¹⁾ n-butyl H H C-84 A¹⁾ tert-butyl H HC-85 A¹⁾ —(CH₂)₄— H H C-86 A¹⁾ 2-ethylhexyl CH₃ H C-87 A¹⁾ n-butyl CH₃ HC-88 A¹⁾ tert-butyl CH₃ H C-89 A¹⁾ 2-ethylhexyl H propyl C-90 A¹⁾n-butyl H propyl C-91 A¹⁾ tert-butyl H propyl C-92 A¹⁾ —(CH₂)₄— H propylC-93 A¹⁾ 2-ethylhexyl CH₃ propyl C-94 A¹⁾ n-butyl CH₃ propyl C-95 A¹⁾tert-butyl CH₃ propyl D-1 B¹⁾ —CH₃ H

D-2 B¹⁾ —CH₃ H

D-3 B¹⁾ —CH₃ H

D-4 B¹⁾ —CH₃ H

D-5 B¹⁾ —CH₃ H

D-6 B¹⁾ —CH₃ H

D-7 B¹⁾ —CH₃ H

D-8 B¹⁾ —CH₃ H

D-9 B¹⁾ —CH₃ H

D-10 B¹⁾ H H

D-12 B¹⁾ H H

D-13 B¹⁾ H H

D-14 B¹⁾ H H

D-15 B¹⁾ H H

D-16 B¹⁾ H H

D-17 B¹⁾ H H

D-18 B¹⁾ H H

D-19 B¹⁾ H H

D-20 B¹⁾ Ph H

D-21 B¹⁾ Ph H

D-22 B¹⁾ Ph H

D-23 B¹⁾ Ph H

D-24 B¹⁾ Ph H

D-25 B¹⁾ Ph H

D-26 B¹⁾ Ph H

D-27 B¹⁾ Ph H

D-28 B¹⁾ Ph H

D-29 B¹⁾

H

D-30 B¹⁾

H

D-31 B¹⁾

H

D-32 B¹⁾

H

D-33 B¹⁾

H

D-34 B¹⁾

H

D-35 B¹⁾

H

D-36 B¹⁾

H

D-37 B¹⁾

H

D-38 B¹⁾

H

D-39 B¹⁾

H

D-40 B¹⁾

H

D-41 B¹⁾

H

D-42 B¹⁾

H

D-43 B¹⁾

H

D-44 B¹⁾

H

D-45 B¹⁾

H

D-46 B¹⁾

H

D-47 B¹⁾

H

D-48 B¹⁾

H

D-49 B¹⁾

H

D-50 B¹⁾

H

D-51 B¹⁾

H

D-52 B¹⁾

H

D-53 B¹⁾

H

D-54 B¹⁾

H

D-55 B¹⁾

H

D-56 B¹⁾

H

D-57 B¹⁾

H

D-58 B¹⁾

H

D-59 B¹⁾

H

D-60 B¹⁾

H

D-61 B¹⁾

H

D-62 B¹⁾

H

D-63 B¹⁾

H

D-64 B¹⁾

H

D-65 B¹⁾

H

D-66 B¹⁾

H

D-67 B¹⁾

H

D-68 B¹⁾

H

D-69 B¹⁾

H

D-70 B¹⁾

H

D-71 B¹⁾

H

D-72 B¹⁾

H

D-73 B¹⁾

H

D-74 B¹⁾

H

D-76 B¹⁾

H

D-78 B¹⁾

H

D-79 B¹⁾

H

D-80 B¹⁾ H H

D-81 B¹⁾ CH₃ H

D-82 B¹⁾ 2-ethylhexyl H H D-83 B¹⁾ n-butyl H H D-84 B¹⁾ tert-butyl H HD-85 B¹⁾ —(CH₂)₄— H H D-86 B¹⁾ 2-ethylhexyl CH₃ H D-87 B¹⁾ n-butyl CH₃ HD-88 B¹⁾ tert-butyl CH₃ H D-89 B¹⁾ 2-ethylhexyl H propyl D-90 B¹⁾n-butyl H propyl D-91 B¹⁾ tert-butyl H propyl D-92 B¹⁾ —(CH₂)₄— H propylD-93 B¹⁾ 2-ethylhexyl CH₃ propyl D-94 B¹⁾ n-butyl CH₃ propyl D-95 B¹⁾tert-butyl CH₃ propyl

²⁾The ligand L^(a) used for the production of comp. C-1 (etc.) ispresent in form of two isomers:

Cpd. R¹ R² R⁴ R⁷ E-1

H H H E-2

H H H E-3

H H H E-4

H H H E-5

H H H E-6

H H H E-7

H H H E-8

H H H E-9

H H H E-10

H

H E-11

H

H E-12

H

H E-13

H

H E-14

H

H E-15

H

H E-16

H

H E-17

H

H E-18

H

H E-19

H

H E-20

H

H E-21

H

H E-22

H

H E-23

H

H E-24

H

H E-25

H

H E-26

H

H E-27

H

H E-28

H

H E-29

H

H E-30

H

H E-31

H

H E-32

H

H E-33

H

H E-34

H

H E-35

H

H E-36

H

H.


8. The compound of the formula I according to claim 1, which is acompound of formula

wherein M² is iridium, R¹ is H, cyclohexyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups, C₁-C₁₈alkyl,

wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, or 5, R¹¹ can be same,or different in each occurrence and is C₁-C₂₅alkyl, C₁-C₂₅alkoxy,—NR²⁵R²⁶, F, or CF₃, R⁴ and R⁷ are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₁-C₁₈alkoxy, whichmay be interrupted by —O—, or —NR²⁵R²⁶; R²⁵ and R²⁶ are independently ofeach other

 R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which mayoptionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and R²⁶together with the nitrogen atom to which they are bonded form a group offormula

 R⁴¹ is H, or C₁-C₂₅alkyl, and L is as defined in claim
 1. 9. Thecompound of the formula I according to claim 1, which is a compound offormula formula LIr(L^(a))₂, or Ir(L^(a))₃, wherein L^(a) is a group offormula

wherein R¹ is H, C₁-C₁₈alkyl, cyclohexyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups,

 wherein n₃ is 0, or an integer 1, 2, 3, 4, or 5, R¹¹ can be same, ordifferent in each occurrence and is C₁-C₂₅alkyl, C₁-C₂₅alkoxy, —NR²⁵R²⁶,F, or CF₃, R² is H, or CH₃, R⁴ and R⁷ are independently of each other H,C₁-C₁₈alkyl, C₁-C₁₈alkyl which is substituted by E and/or interrupted byD, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by —NR²⁵R²⁶, C₁-C₁₈alkoxywhich may be interrupted by —O—, or —NR²⁵R²⁶; R²⁵ and R²⁶ areindependently of each other

 R¹¹⁶ and R¹¹⁷ are independently of each other C₁-C₂₅alkyl, which mayoptionally be interrupted by —O—, or C₁-C₂₅alkoxy; or R²⁵ and R²⁶together with the nitrogen atom to which they are bonded form a group offormula

 R⁴¹ is H, or C₁-C₂₅alkyl, and L is as defined in claim
 1. 10. Thecompound of the formula I according to claim 1, which is a compound offormula

wherein R¹ is C₂-C₁₀alkyl, cyclohexyl, which can optionally besubstituted by one to three C₁-C₄alkyl groups, R² is H, or CH₃, and L is


11. An organic electronic device, comprising an emitting layer whereinthe emitting layer comprises a compound according to claim
 1. 12. Thedevice of claim 11, further comprising a hole transport layer selectedfrom polyvinyl-carbazol,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC),N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl-4-N,N-diphenylaminostyrene (TPS),p-(diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine(TPA), bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane(MPMP),1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),N,N′-di-α-naphthyl-N,N′-diphenyl-4,4′-diphenyldiamine (α-NPD),porphyrinic compounds, and combinations thereof, or electrontransportingmaterials, selected from tris(8-hydroxyquinolato)aluminium (Alq3),bis(2-methyl-8-hydroxyquinaolato)(p-phenylphenolato)aluminium (BAlq),tetrakis(8-hydroxyquinolato)zirconium (ZrQ) and mixtures thereof.
 13. Anelectronic device comprising a compound according to claim 1 whichelectronic device is a organic light emitting diodes (OLEDs), as oxygensensitive indicators, as phosphorescent indicators in bioassays, orcatalysts.
 14. Compounds of formula

wherein X is H, methyl, or ethyl, and L^(a) is

wherein R₁, R₂, R_(1′), R³, R⁴, R^(3′), R^(4′), R⁵, R⁶, R^(5′), R^(6′),R⁷, R⁸, R^(7′) and R^(8′) are as defined in claim 1, with the provisothat at least one of R¹, R², R³, R⁸, R⁴, R⁷, R⁵ and R⁶ is different fromH and the further proviso that a compound of formula

wherein L^(a) is

a compound of formula

wherein L^(a) is

and a compound of formula

wherein L^(a) is

are excluded.